A method for analyzing odor components of environmental smoke

Abstract

The present application relates to the technical field of chemical component analysis in environmental flue gas, and specifically, to a method for analyzing odor components in environmental flue gas. The method comprises the following steps: 1) overall sniffing of environmental tobacco smoke; 2) sampling; 3) analysis of characteristic odor components: 4) analysis of key odor components. The present invention can achieve the enrichment of low-concentration odor compounds. After sampling, thermal desorption analysis is directly performed without complicated pre-treatment. The method is simple, rapid, reproducible, and highly sensitive, and can fully meet the analysis requirements of odor components in environmental flue gas; by diluting the sampled sample, key odor substances can be determined, and accurate identification of odor components in environmental flue gas can be achieved; it is more suitable for odor analysis of complex samples, and can purposefully cut the odor characteristics of interest, effectively removing the interference of odorless or lightly smelled but high-content compounds, and is more selective and efficient.

Description

Technical Field

[0001] The present application relates to the technical field of chemical component analysis in environmental flue gas, and in particular, to a method for analyzing odor components in environmental flue gas. Background Art

[0002] Environmental tobacco smoke (ETS) is a complex chemical mixture produced by the burning of tobacco products. It comes from the sidestream smoke (75%) produced when tobacco products are burned and the mainstream smoke (15%) exhaled by smokers. ETS is formed after the smoke is highly diluted and aged by air. Studies have shown that ETS is an important source of air quality pollution and has certain hazards to human health. At present, the research on ETS pollution to the environment mainly focuses on the qualitative and quantitative analysis of chemical components.

[0003] The odor components in ETS are material components that humans can directly perceive and are closely related to air quality. Studying the odor components in ETS is of great significance for correctly understanding and evaluating the environmental odor pollution caused by environmental smoke. However, there are few reports on the research of odor components in ETS.

[0004] Odor research usually uses gas chromatography-mass spectrometry / olfaction (GC-MS / O) technology, which is mainly used in food, tobacco, flavors and fragrances, and environmental monitoring. This technology combines precision instrument analysis with the human sense of smell to identify odor active ingredients.

[0005] The composition of environmental smoke is complex and the content of compounds is low after high dilution (ug / m 3 If a conventional one-dimensional GC-MS / O instrument is used for analysis, it only has a single polarity analytical column and limited chromatographic analysis capabilities, resulting in poor separation of odor compounds and the presence of odor co-elution, which cannot meet the odor analysis needs of environmental flue gas ETS species. If a two-dimensional GC-MS / O instrument is used for analysis, although the instrument's analysis capabilities are improved, the instrument's injection method is solid phase microextraction (SPME) or solvent extraction, which is limited by the extraction capacity, the selective adsorption of the extraction head, and the injection volume, and has limited sensitivity. It is also impossible to achieve effective analysis of environmental flue gas odor components, and there are currently no related research reports on ETS odor component analysis. Summary of the invention

[0006] In view of the shortcomings of the prior art described above, in order to solve the technical problem that the instrumental analysis sensitivity of the odor components of environmental tobacco smoke in the prior art is low and cannot be effectively analyzed, the purpose of the present invention is to provide an analysis method for the odor components of environmental smoke, which is used to solve the problems in the prior art.

[0007] To achieve the above-mentioned and other related purposes, the present application provides, on the one hand, a method for analyzing the odor components of environmental smoke, the method comprising the following steps:

[0008] 1) Overall sniffing of environmental tobacco smoke: Perform a first artificial sniff in a space where environmental tobacco smoke exists to obtain one or more preliminary characteristic smells, and score each of the preliminary characteristic smells;

[0009] 2) Sampling: extracting the ambient tobacco smoke in the space described in step 1), and adsorbing it with an adsorbent to obtain a sample;

[0010] 3) Characteristic odor component analysis: The sample described in step 2) is subjected to thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis, combined with the preliminary characteristic smell described in step 1), the peak time and odor characteristics of the characteristic odor components of the ambient smoke smelled are recorded, and the odor compounds are detected by mass spectrometry;

[0011] 4) Analysis of key odor components: The characteristic odor components of the ambient smoke obtained in step 3) are diluted by shortening the sampling time, and analyzed by the thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis method of step 3). When the characteristic odor components of the ambient smoke cannot be perceived by sniffing, the dilution factor is obtained.

[0012] On the other hand, the present application provides an environmental flue gas odor component analysis device, comprising a sampling tube, a cold trap, a first chromatographic column, a second chromatographic column and a mass spectrometer detector connected in sequence; the sampling tube and the cold trap are arranged in a thermal desorption instrument; the first chromatographic column and the second chromatographic column are arranged in a column oven; a CO2 cooling valve is also provided on the connecting pipeline between the first chromatographic column and the second chromatographic column; it also includes an odor identification port, which is connected to the first chromatographic column and the second chromatographic column respectively; it also includes a hydrogen flame ionization detector, which is connected to the first chromatographic column.

[0013] On the other hand, the present application provides the use of an environmental smoke odor component analysis device in environmental smoke odor analysis.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] 1. This application uses a sampling tube with an adsorbent to adsorb and enrich the odor components of environmental flue gas, so as to increase the analytical concentration of odor compounds and achieve the enrichment of low-concentration odor compounds; after sampling, the sampling tube directly performs thermal desorption analysis without complex pretreatment. The method is simple, fast, reproducible, and highly sensitive, and can fully meet the analysis requirements of odor components in environmental flue gas.

[0016] 2. The multidimensional gas chromatography-mass spectrometry olfactory device constructed in this application improves the separation ability and detection sensitivity of the instrument by connecting two chromatographic columns of different polarities in series and cooling and focusing carbon dioxide. It is equipped with three detectors, including a hydrogen flame ionization detector, a mass spectrometer, and a human nose. The olfactory mouth has no co-effluent, so that the odor compounds in complex environmental smoke can be fully separated, thereby realizing accurate identification of odor components in environmental smoke.

[0017] 3. By changing the sampling time, the sample can be diluted. The dilution factor can be determined by smelling, and the key odor substances can be determined. The key odor substances are important components of odor pollution caused by environmental smoke, and accurate analysis and judgment of odor pollution caused by environmental smoke can be achieved.

[0018] 4. Compared with one-dimensional gas chromatography-mass spectrometry olfactory analysis technology, the present application has better analysis effect on complex matrix samples and is more suitable for odor analysis of complex samples. It can purposefully cut the odor characteristics of concern, such as in the analysis of environmental smoke of external flavor cigarettes, such as mint cigarettes and milk-flavored cigarettes; effectively remove the interference of odorless or lightly smelled but high-content compounds in environmental smoke, such as nicotine, and is more selective and efficient, effectively avoiding the olfactory detective from sniffing for a long time, and achieving the enrichment and qualitative detection of odorous and trace components. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Shown is a schematic diagram of an environmental flue gas odor component analysis device.

[0020] Figure 2 Shown is a radar chart of the overall sensory olfactory evaluation of domestic cigarette environment smoke.

[0021] Figure 3 Shown is the mass spectrum of the first cut segment of domestic cigarette environmental smoke.

[0022] Figure 4 Shown is the mass spectrum of the second cut segment of domestic cigarette environmental smoke.

[0023] Figure 5 Shown is a radar chart of the overall sensory olfactory evaluation of ambient smoke from mixed cigarettes.

[0024] Figure 6 Shown is the mass spectrum of the first cut section of mixed cigarette ambient smoke.

[0025] Figure 7 Shown is the mass spectrum of the second cut section of mixed cigarette ambient smoke.

[0026] Figure 8 Shown is a radar chart of the overall sensory olfactory evaluation of ambient smoke from menthol cigarettes.

[0027] Fig. 9 Shown is a partial flame ionization detector chromatogram of a menthol cigarette.

[0028] Fig.10 Shows the mass spectrum of the cut segments that produce the mint flavor of menthol cigarettes.

[0029] Fig.11 Shown is a mass spectrum obtained by using conventional GC-MS detection of the environmental flue gas sample in Comparative Example 1 of the present invention.

[0030] Component number description:

[0031] 1 Thermal desorption instrument

[0032] 11 Cold Trap

[0033] 12 Sampling tube

[0034] 2 Column oven

[0035] 21 First gas chromatography column

[0036] 211 Injection end of the first gas chromatography column

[0037] 212 Sample outlet of the first gas chromatography column

[0038] 22 Second GC column

[0039] 221 Injection end of the second gas chromatography column

[0040] 222 Sample outlet of the second gas chromatography column

[0041] 23 CO2 cooling valve

[0042] 3 Hydrogen flame ionization detector

[0043] 4 Mass spectrometer detector

[0044] 5. Smell mouth DETAILED DESCRIPTION

[0045] In order to make the invention purpose, technical scheme and beneficial effect of the present invention clearer, the present invention is further described below in conjunction with examples. It should be understood that the examples are only used to explain the present invention and are not used to limit the scope of the present invention. The test methods used in the following examples are conventional methods unless otherwise specified, and those familiar with the technology can easily understand other advantages and effects of the present invention from the contents disclosed in this description.

[0046] After extensive exploration and research, the inventors of the present invention discovered a method for analyzing odor components in environmental flue gas based on thermal desorption-multidimensional gas chromatography-mass spectrometry olfaction technology. By building a thermal desorption and multidimensional gas chromatography-mass spectrometry olfaction system, a thermal desorption-multidimensional gas chromatography-mass spectrometry analysis method for odor components in environmental flue gas was established for the first time to meet the needs of odor component analysis in environmental flue gas. On this basis, the present invention was completed.

[0047] The present application provides a method for analyzing the odor components of environmental smoke, the method comprising the following steps:

[0048] 1) Overall sniffing of environmental tobacco smoke: Perform a first artificial sniff in a space where environmental tobacco smoke exists to obtain one or more preliminary characteristic smells, and score each of the preliminary characteristic smells;

[0049] 2) Sampling: extracting the ambient tobacco smoke in the space described in step 1), and adsorbing it with an adsorbent to obtain a sample;

[0050] 3) Characteristic odor component analysis: The sample described in step 2) is subjected to thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis, combined with the preliminary characteristic smell described in step 1), the peak time and odor characteristics of the characteristic odor components of the ambient smoke smelled are recorded, and the odor compounds are detected by mass spectrometry;

[0051] 4) Analysis of key odor components: The characteristic odor components of the ambient smoke obtained in step 3) are diluted by shortening the sampling time, and analyzed by the thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis method of step 3). When the characteristic odor components of the ambient smoke cannot be perceived by sniffing, the dilution factor is obtained.

[0052] In a method for analyzing the odor components of environmental smoke provided by the present application, step 1) is the overall sniffing of the environmental tobacco smoke: the first artificial sniffing is performed in a space where environmental tobacco smoke exists, one or more preliminary characteristic smells are obtained, and each of the preliminary characteristic smells is scored. The sniffing is a method conventionally used in the tobacco field, in which an artificial sensory sniffing is performed at a sniffing port, that is, an olfactory analysis of the odor components of environmental smoke is performed by an olfactory inspector with good olfactory perception and good health. The odor description includes a variety of stinky, sour, smoky, burnt, and other flavors. The other flavors include mint, milk, coffee, and the like. The scoring can be a multi-point system, preferably a 7-point scoring system, and the scores are from 1 to 7 according to the odor intensity from weak to strong.

[0053] In a method for analyzing the odor components of environmental smoke provided by the present application, step 2) is sampling: extracting the environmental tobacco smoke in the space described in step 1), and obtaining a sample after adsorbing it with an adsorbent. The sampling can be, for example, through an air sampling device, preferably, an air sampling pump. The sampling tube is made of glass material, and the adsorbent is selected from one or more of TenaxTA, graphitized carbon black, activated carbon, and molecular sieves. Preferably, the adsorbent type is Tenax TA. Sampling with a sampling tube with an adsorbent facilitates the capture and adsorption of environmental smoke, so as to increase the analytical concentration of odor compounds and achieve the enrichment of low-concentration odor compounds, so that samples of environmental smoke can be obtained even in an environment with lower concentrations, which is convenient for subsequent analysis.

[0054] In step 2) of the present application, the sampling time is 5 to 60 min, preferably 5 to 30 min, 30 to 50 min, or 50 to 60 min, etc. The sampling flow rate is 50 to 500 mL / min, preferably 50 to 200 ml / min, 200 to 400 ml / min, 400 to 500 ml / min, etc. Preferably, the sampling time is 30 min and the sampling flow rate is 200 ml / min.

[0055] In the method for analyzing the odor components of environmental smoke provided by the present application, step 3) is the analysis of characteristic odor components: the sample described in step 2) is subjected to thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis, combined with the preliminary characteristic taste described in step 1), the peak time and odor characteristics of the characteristic odor components of environmental smoke smelled are recorded, and the odor compounds are detected by mass spectrometry. Step 4) is the analysis of key odor components: the characteristic odor components of environmental smoke obtained in step 3) are diluted by shortening the sampling time, and the thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis method of step 3) is used for analysis. When the characteristic odor components of environmental smoke cannot be perceived by smell, the dilution factor is obtained.

[0056] In a specific embodiment of the present application, the thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis step includes: first performing thermal desorption, then sampling through a first gas chromatography column for separation, hydrogen flame ionization detector detection, and a second artificial olfactory analysis, and based on the combination of the preliminary characteristic smell in step 1) and the second artificial olfactory analysis, determining the cutting time period of the required characteristic smell; after sampling again through the first gas chromatography column for separation, selecting the cutting time period and then separating through the second gas chromatography column, respectively, and detecting by a mass spectrometer and performing a third artificial olfactory analysis to determine the characteristic odor components of the ambient smoke.

[0057] In a specific embodiment of the present application, the multidimensional gas chromatography uses two gas chromatography columns, the first chromatographic column is a non-polar chromatographic column, and the second chromatographic column is a polar chromatographic column. Preferably, the first chromatographic column is selected from SGE-BPX5 gas chromatography column, Agilent DB-1ms gas chromatography column, or Agilent DB-5ms gas chromatography column; the second chromatographic column is selected from Solgel-wax gas chromatography column, Agilent DB-wax gas chromatography column, or DB-FFAP gas chromatography column.

[0058] In step 3) or step 4) of the present application, the thermal desorption conditions are:

[0059] The primary thermal desorption temperature is 270-300°C, preferably 270-280°C, 280-290°C, 290-300°C, etc.

[0060] The desorption time is 6 to 10 minutes, preferably 6 to 8 minutes, 8 to 10 minutes, etc.

[0061] The desorption flow rate is 15 to 100 ml / min, preferably 15 to 20 ml / min, 20 to 50 ml / min, 50 to 100 ml / min, etc.

[0062] The cold trap adsorption temperature is -40 to 20°C; preferably -40 to -20°C, -20 to 10°C, 10 to 20°C, etc.

[0063] The secondary desorption temperature is 270-300°C, preferably 270-280°C, 280-290°C, 290-300°C, etc.

[0064] The desorption time is 10 to 15 minutes, preferably 10 to 12 minutes, 12 to 15 minutes, etc.

[0065] Preferably, the thermal desorption conditions are:

[0066] The primary thermal desorption temperature was 280 °C and the desorption time was 10 min;

[0067] The desorption flow rate was 20 ml / min;

[0068] The secondary desorption temperature was 300 °C and the desorption time was 15 min.

[0069] In step 3) or step 4) of the present application, the temperature raising program of the first chromatographic column is: maintain at 40-60°C for 1-5 min, then increase the temperature to 200-230°C at a rate of 2-10°C / min, and maintain for 5-20 min.

[0070] In step 3) or step 4) of the present application, the heating program of the second chromatographic column is: maintain at 40-50°C for 1-5 min, then increase the temperature to the required temperature for the cutting time period at a rate of 4-8°C / min, then cool down to 40-50°C at a cooling rate of 20-120°C / min and maintain for 1-5 min, then increase the temperature to 230-250°C at a rate of 2-7°C / min and maintain for 10-30 min.

[0071] In a specific embodiment of the present application, the cutting time period is determined by determining the retention time period in the gas chromatogram obtained by detecting the corresponding component with a hydrogen flame ionization detector corresponding to the odor component to be detected by olfactory analysis at the olfactory port. The cutting time period selection sets the retention time between the peaks and valleys in the gas chromatogram as the cutting time period, wherein a wider cutting time period is set in an area with fewer chromatographic peaks and lower content, and vice versa, a narrower cutting time period is set.

[0072] In step 3) or step 4) of the present application, the mass spectrometry conditions are:

[0073] Transmission line temperature: 230-250°C; preferably 230-240°C, 240-250°C, etc.

[0074] Ionization energy: 65-75 eV; preferably 65-70 eV, 70-75 eV, etc.

[0075] EI source temperature: 220-250°C; preferably 220-230°C, 230-240°C, 240-250°C, etc.

[0076] Quadrupole temperature: 140-150°C; preferably 140-142°C, 142-145°C, 145-150°C, etc.

[0077] Mass scanning range: 33-300amu; preferably 33-66amu, 66-100amu, 100-200amu, 200-300amu, etc.

[0078] The mass spectrometry qualitative analysis method is selected from one or both of the following: NIST mass spectrometry library retrieval compound structure qualitative analysis and Wiely mass spectrometry library retrieval compound structure qualitative analysis.

[0079] Preferably, the mass spectrometry conditions are:

[0080] Transmission line temperature: 240°C;

[0081] Ionization energy: 70 eV;

[0082] EI source temperature: 240°C;

[0083] Quadrupole temperature: 150°C;

[0084] Mass scanning range: 33~300amu.

[0085] In step 3) or step 4) of the present application, the olfactory analysis is used to record the peak time and odor characteristics of the odor components.

[0086] In step 4) of the present application, the sampling time is 3s to 30min, preferably 3 to 15s, 15 to 60s, 1 to 1.2min, 1.2 to 6min, 6 to 30min, etc. The sampling flow rate is 50 to 500mL / min, preferably 50 to 500ml / min, 50 to 200ml / min, 200 to 400ml / min, 400 to 500ml / min, etc. Preferably, the sampling times for dilution analysis are 30min, 6min, 1.2min, 15s and 3s, respectively. The dilution multiple is obtained according to the ratio between the initial sampling time and the shortened sampling time, and the dilution multiple is the dilution factor. Specifically, when the initial sampling time is 30min and the shortened sampling time is 6min, the dilution factor is 5. The larger the dilution factor, the greater the contribution of the compound to the overall odor of the environmental smoke. By changing the sampling time, the sample is diluted and the dilution factor is determined by smelling. The key odor substances can be identified. The key odor substances are important components of odor pollution caused by environmental smoke. There is no co-exudate from the olfactory identification port, which enables accurate identification of odor components in environmental smoke.

[0087] The present application also provides an environmental smoke odor component analysis device, such as Figure 1 As shown, it includes a sampling tube 12, a cold trap 11, a first chromatographic column 21, a second chromatographic column 22 and a mass spectrometer 4 which are connected in sequence; the sampling tube 12 and the cold trap 11 are arranged in a thermal desorption instrument 1; the first chromatographic column 21 and the second chromatographic column 22 are arranged in a column oven 2; a CO2 cooling valve 23 is also arranged on the connecting device between the first chromatographic column 21 and the second chromatographic column 22; it also includes an olfactory port 5, which is connected to the first chromatographic column 21 and the second chromatographic column 22 respectively; it also includes a hydrogen flame ionization detector 3, which is connected to the first chromatographic column 21. By connecting two chromatographic columns of different polarities in series and cooling and focusing carbon dioxide, the separation ability and detection sensitivity of the instrument are improved, and three detectors are equipped, including a hydrogen flame ionization detector, a mass spectrometer detector, and a human nose, so that the odor compounds in the complex environmental smoke can be fully separated.

[0088] In a specific embodiment of the present application, the cold trap 11 is connected to the first chromatographic column 21 through the injection end 211 of the first chromatographic column. The hydrogen flame ionization detector 3 and the olfactory port 5 are both connected to the first chromatographic column 21 through the sample outlet 212 of the first chromatographic column. The sample outlet 212 of the first chromatographic column is connected to the second chromatographic column 22 through the injection end 221 of the second chromatographic column. The mass spectrometer detector 4 and the olfactory port 5 are both connected to the second chromatographic column 22 through the sample outlet 222 of the second chromatographic column.

[0089] In a specific embodiment of the present application, the thermal desorption instrument 1 can realize adsorption and thermal desorption of ambient flue gas. Specifically, the ambient flue gas is adsorbed by the adsorbent in the sampling tube 12, and then desorbed by first heating up, then adsorbed by cooling through the cold trap 11, and then heated up and desorbed again, thereby facilitating the analysis of odor components in ambient flue gas with lower concentrations.

[0090] In a specific embodiment of the present application, the column oven 2 can perform multidimensional gas chromatography analysis on the odor components of the ambient smoke after thermal desorption. First, a one-dimensional program is used to obtain a cutting time period by the hydrogen flame ionization detector 3 and the olfactory port 5, and then a two-dimensional program is performed according to the cutting time period to obtain a peak diagram of the specific ambient smoke odor components by the mass spectrometer detector 4 and the olfactory port 5, and combined with the overall olfactory smell of the ambient smoke, the characteristic analysis and corresponding compounds of the ambient smoke odor components are obtained. Compared with the one-dimensional gas chromatography-mass spectrometry olfactory analysis technology, it has a better analysis effect on complex matrix samples and is more suitable for the odor analysis of complex samples. It can purposefully cut the odor characteristics of concern, effectively remove the interference of compounds with no odor or a light odor but a high content in the ambient smoke, such as nicotine, and is more selective and efficient, effectively avoiding the olfactory detective from sniffing for a long time, and achieving the enrichment and qualitative detection of odorous and trace components.

[0091] In a specific embodiment of the present application, the CO2 cooling valve 23 is opened 1 to 5 minutes before the start of the cutting time period and is closed before the next temperature increase to facilitate cooling of the focusing compound.

[0092] The present application also provides the use of the environmental smoke odor component analysis device in environmental smoke odor analysis. When there is environmental smoke, the method can be used to analyze the odor in the environmental smoke, thereby obtaining a rational index for environmental smoke evaluation.

[0093] As described above, the present application provides an analysis method for the odor components of ambient smoke. The olfactory expert performs an overall olfactory evaluation of the ambient smoke. The ambient smoke is sampled and enriched through a sampling tube. Thermal desorption and multidimensional gas chromatography-mass spectrometry olfaction are used to develop an analysis method for the odor components in ambient smoke for the first time, realize the odor characteristic analysis of the odor components in ambient smoke, and determine the key odor components that affect ambient smoke. This determination method is the first to establish a full component determination method for odor components in ambient smoke.

[0094] In the method for analyzing the odor components of environmental smoke provided by the present invention:

[0095] 1. Use a sampling tube with an adsorbent to adsorb and enrich the odor components of environmental flue gas to increase the analytical concentration of odor compounds and achieve the enrichment of low-concentration odor compounds. After sampling, the sampling tube directly performs thermal desorption analysis without complex pre-treatment. The method is simple, fast, reproducible, and highly sensitive, and can fully meet the analysis requirements of odor components in environmental flue gas.

[0096] 2. The multi-dimensional gas chromatography-mass spectrometry olfactory device built improves the separation ability and detection sensitivity of the instrument by connecting two chromatographic columns of different polarities in series and cooling and focusing carbon dioxide. It is equipped with three detectors, including a hydrogen flame ionization detector, a mass spectrometer, and a human nose. There is no co-effluent in the olfactory mouth, so that the odor compounds in complex environmental smoke can be fully separated, thereby realizing the accurate identification of odor components in environmental smoke.

[0097] 3. By changing the sampling time, the sample can be diluted. The dilution factor can be determined by smelling, and the key odor substances can be determined. The key odor substances are important components of odor pollution caused by environmental smoke, and accurate analysis and judgment of odor pollution caused by environmental smoke can be achieved.

[0098] 4. Compared with one-dimensional gas chromatography-mass spectrometry olfactory analysis technology, it has better analysis effect on complex matrix samples and is more suitable for odor analysis of complex samples. It can purposefully cut the odor characteristics of concern, such as in the analysis of environmental smoke of external flavor cigarettes, such as mint cigarettes and milk-flavored cigarettes; effectively remove the interference of odorless or lightly smelled but high-content compounds in environmental smoke, such as nicotine, which is more selective and efficient, effectively avoiding the olfactory detective from sniffing for a long time, and achieving the enrichment and qualitative detection of odorous and trace components.

[0099] The invention of the present application is further described below by way of examples, but the scope of the present application is not limited thereby.

[0100] The materials and instruments used in the following examples are as follows:

[0101] Materials: Tenax TA, Carbotrap, activated carbon glass sampling tube (1 / 4 inch diameter, 3.5 inches length, Supelco, USA). Finished cigarettes (including domestic flue-cured tobacco, foreign flue-cured tobacco, blended cigarettes and menthol cigarettes) are all commercially available products.

[0102] Instruments: TurboMatrix ATD thermal desorber (Perkin Elmer, USA); 7890B / 5977A GC-MS coupling instrument (Agilent, USA); CDS Model 9600 sampling tube aging device (CDS Analytical, USA); SIAA-CYY-2 dual-channel gas sampling instrument (Shanghai Anpu Experimental Technology Co., Ltd.).

[0103] Example 1

[0104] 1. Overall smell of ambient smoke:

[0105] A domestic flue-cured tobacco was placed in a 40cm×23cm×24cm simulated environmental smoke chamber and smoldered under static non-ventilated conditions. After the smoldering ended, the fan was turned on for 2 minutes to form ETS. The odor detectors sniffed the gas in the environmental smoke chamber containing ETS, described the characteristics of the odor they felt, and scored the intensity of each characteristic odor on a seven-point scale.

[0106] 2. The sampling tube enriches the odor components of environmental smoke:

[0107] After the overall sniffing, connect one end of the sampling tube containing Tenax TA adsorbent to the air sampling pump and extract air at a flow rate of 200 ml / min for 30 minutes to collect ETS. After the sampling is completed, cover the two ends of the sampling tube with Teflon caps and store at room temperature for analysis.

[0108] 3. Analysis of characteristic odor components:

[0109] Thermal desorber conditions: carrier gas: helium (≥99.999%); primary desorption temperature: 270°C; primary desorption time: 10 min; desorption flow rate: 20 ml / min; cold trap adsorption temperature: -40°C; secondary desorption temperature: 300°C; secondary desorption time: 10 min;

[0110] Gas chromatography conditions: First chromatographic column: BPX5 capillary column (30m×0.53mm×0.5μm); Second chromatographic column: SolGel-wax capillary column (30m×0.53mm×0.5μm); Carrier gas: Helium (≥99.999%); Chromatographic temperature program. One-dimensional analysis: 50℃ for 2min, then heated to 210℃ at a rate of 7℃ / min and kept for 10min. Two-dimensional analysis: Cutting segment 1: 50℃ for 2min, then heated to 78℃ at a rate of 7℃ / min, then cooled to 50℃ at 120℃ / min and kept for 2min, then heated to 250℃ at 3℃ / min and kept for 30min. Cutting section 2: 50℃ for 2min, then increase to 106℃ at a rate of 7℃ / min, then cool down to 50℃ at 120℃ / min and keep for 2min, then increase to 250℃ at 3℃ / min and keep for 30min. Cutting section 3: 50℃ for 2min, then increase to 141℃ at a rate of 7℃ / min, then cool down to 50℃ at 120℃ / min and keep for 2min, then increase to 250℃ at 3℃ / min and keep for 30min. Cutting section 4: 50℃ for 2min, then increase to 190℃ at a rate of 7℃ / min, then cool down to 50℃ at 120℃ / min and keep for 2min, then increase to 250℃ at 3℃ / min and keep for 30min. The cutting times corresponding to the four cutting sections are 1 to 6min, 6 to 10min, 10 to 15min, and 15 to 20min, respectively. The CO2 cooling valve is opened 1min before the start of the cutting time period to cool the focusing compound.

[0111] Mass spectrometry conditions: transfer line temperature: 230°C; ionization energy: 70 eV; EI source temperature: 230°C; quadrupole temperature: 150°C; mass scanning range: 33-300 amu.

[0112] The ETS sampling tube was subjected to thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis. The odorist sniffed at the olfactory port and recorded the peak time and odor characteristics of the odor components smelled. At the same time, the compound was qualitatively identified by the mass spectrometry library.

[0113] 4. Analysis of key odor components:

[0114] The dilution injection effect was achieved by shortening the sampling time of the sampling tube. The sampling times were 30 min, 6 min, 1.2 min, 15 s and 3 s respectively. The obtained sampling tube was analyzed according to step 3.

[0115] The overall smell of domestic flue-cured tobacco ETS is as follows Figure 2 As shown, its burnt aroma, stinky smell and smoked smell are quite obvious.

[0116] The search results were qualitatively analyzed by mass spectrometry database retrieval. The mass spectrometry database was the NIST database. The component judgment was based on the matching degree ≥ 85. Combined with the smell characteristics of the smell, a total of 83 odor components were determined for the characteristic odor components of domestic cigarettes, including 8 olefins, 18 nitrogen heterocyclics, 15 oxygen heterocyclics, 15 phenols, 9 aromatics, 2 amines, 8 acids, and 8 others. Different compounds have different odor characteristics, such as trimethylamine (amine odor, fishy smell), 2-methylpyrazine (chocolate, sweet fragrance), isovaleric acid (corruption, sour smell), metacresol (smoked, medicinal smell), maltol (burnt sweet, nut fragrance), etc. The odor characteristics and dilution factors of the odor compounds of the first cutting section shown in Table 1 are obtained according to the ratio between the initial sampling time and the shortened sampling time. The dilution multiple is the dilution factor. Specifically, when the initial sampling time is 30min and the shortened sampling time is 6min, the dilution factor is 5. The larger the dilution factor, the greater the contribution of the compound to the overall odor of ambient smoke. Compounds with larger dilution factors are key odor components, such as trimethylamine, 3-methyl-2-cyclopentene-1-one, 2-acetylfuran, etc. Figure 3 Display the mass spectrum of the first cut segment. Figure 4 The mass spectrum of the second cut segment is displayed.

[0117] Table 1 Odor components and odor characteristics of the first cut section in domestic cigarette environmental smoke and their dilution factors

[0118]

[0119]

[0120] Example 2

[0121] 1. Overall smell of ambient smoke:

[0122] A blended cigarette was placed in a 40cm×23cm×24cm simulated environmental smoke chamber and smoldered under static, unventilated conditions. After the smoldering ended, the fan was turned on for 2 minutes to form ETS. The odor detectives sniffed the gas in the environmental smoke chamber containing ETS, described the characteristics of the odor they felt, and scored the intensity of each characteristic odor on a seven-point scale.

[0123] 2. Enrichment of environmental smoke odor components with sampling tubes: After the overall sniffing is completed, connect one end of the sampling tube containing Tenax TA adsorbent to the air sampling pump, and extract air at a flow rate of 200ml / min for 30min to collect ETS. After sampling, cover both ends of the sampling tube with Teflon caps and store at room temperature for analysis.

[0124] 3. Analysis of characteristic odor components: Thermal desorber conditions: carrier gas: helium (≥99.999%); primary desorption temperature: 270°C; primary desorption time: 10 min; desorption flow rate: 20 ml / min; cold trap adsorption temperature: -40°C; secondary desorption temperature: 300°C; secondary desorption time: 10 min;

[0125] Gas chromatography conditions: First chromatographic column: BPX5 capillary column (30m×0.53mm×0.5μm); Second chromatographic column: SolGel-wax capillary column (30m×0.53mm×0.5μm); Carrier gas: Helium (≥99.999%); Chromatographic temperature program. One-dimensional analysis: 50℃ for 2min, then heated to 220℃ at a rate of 7℃ / min and kept for 20min. Two-dimensional analysis: Cutting segment 1: 50℃ for 2min, then heated to 78℃ at a rate of 7℃ / min, then cooled to 50℃ at 120℃ / min and kept for 2min, then heated to 250℃ at 3℃ / min and kept for 30min. Cutting section 2: 50℃ for 2min, then increase to 106℃ at a rate of 7℃ / min, then cool down to 50℃ at 120℃ / min and keep for 2min, then increase to 250℃ at 3℃ / min and keep for 30min. Cutting section 3: 50℃ for 2min, then increase to 141℃ at a rate of 7℃ / min, then cool down to 50℃ at 120℃ / min and keep for 2min, then increase to 250℃ at 3℃ / min and keep for 30min. Cutting section 4: 50℃ for 2min, then increase to 190℃ at a rate of 7℃ / min, then cool down to 50℃ at 120℃ / min and keep for 2min, then increase to 250℃ at 3℃ / min and keep for 30min. The cutting times corresponding to the four cutting sections are 1 to 6min, 6 to 10min, 10 to 15min, and 15 to 20min, respectively. The CO2 cooling valve is opened 1min before the start of the cutting time period to cool the focusing compound.

[0126] Mass spectrometry conditions: transfer line temperature: 230°C; ionization energy: 70 eV; EI source temperature: 230°C; quadrupole temperature: 150°C; mass scanning range: 33-300 amu.

[0127] The ETS sampling tube was subjected to thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis. The odorist sniffed at the olfactory port and recorded the peak time and odor characteristics of the odor components smelled. At the same time, the compound was qualitatively identified by the mass spectrometry library.

[0128] 4. Analysis of key odor components: The dilution injection effect was achieved by shortening the sampling time of the sampling tube. The sampling times were 30 min, 6 min, 1.2 min, 15 s and 3 s respectively. The obtained sampling tube was analyzed according to step 3.

[0129] The overall smell of ETS of mixed cigarettes is as follows Figure 5 As shown, the overall odor intensity is relatively strong, with the stench and burnt smell being very prominent, followed by the smoked smell.

[0130] The search results were qualitatively analyzed by mass spectrometry database retrieval. The mass spectrometry database was the NIST database. The component judgment was based on a match degree ≥ 85. Combined with the odor characteristics of sniffing, a total of 83 odor components were identified for the characteristic odor components of mixed cigarettes, including 8 olefins, 18 nitrogen heterocyclics, 15 oxygen heterocyclics, 15 phenols, 9 aromatics, 2 amines, 8 acids, and 8 others. The mass spectrum of the first cut of ETS of mixed cigarettes is shown in the figure below: Figure 6 The mass spectrum of the second cut section of ETS of mixed cigarettes is shown in Figure 7 shown.

[0131] Example 3

[0132] 1. Overall smell of ambient smoke:

[0133] A menthol cigarette was placed in a 40cm×23cm×24cm simulated environmental smoke chamber and smoldered under static, unventilated conditions. After the smoldering ended, the fan was turned on for 2 minutes to form ETS. The odor detectives sniffed the gas in the environmental smoke chamber containing ETS, described the characteristics of the odor they felt, and scored the intensity of each characteristic odor on a seven-point scale.

[0134] 2. Enrichment of environmental smoke odor components with sampling tubes: After the overall sniffing is completed, connect one end of the sampling tube containing Tenax TA adsorbent to the air sampling pump, and extract air at a flow rate of 200ml / min for 30min to collect ETS. After sampling, cover both ends of the sampling tube with Teflon caps and store at room temperature for analysis.

[0135] 3. Analysis of characteristic odor components: Thermal desorber conditions: carrier gas: helium (≥99.999%); primary desorption temperature: 270°C; primary desorption time: 10 min; desorption flow rate: 20 ml / min; cold trap adsorption temperature: -40°C; secondary desorption temperature: 300°C; secondary desorption time: 10 min;

[0136] Gas chromatography conditions: First chromatographic column: BPX5 capillary column (30m×0.53mm×0.5μm); Second chromatographic column: SolGel-wax capillary column (30m×0.53mm×0.5μm); Carrier gas: Helium (≥99.999%); Chromatographic temperature program. One-dimensional analysis: 50℃ for 2min, then heated to 200℃ at a rate of 7℃ / min and kept for 5min. Two-dimensional analysis: Cutting segment 1: 50℃ for 2min, then heated to 78℃ at a rate of 7℃ / min, then cooled to 50℃ at 120℃ / min and kept for 2min, then heated to 250℃ at 3℃ / min and kept for 30min. Cutting section 2: 50°C for 2 min, then increase to 106°C at a rate of 7°C / min, then cool down to 50°C at 120°C / min and keep for 2 min, then increase to 250°C at 3°C / min and keep for 30 min. Cutting section 3: 50°C for 2 min, then increase to 141°C at a rate of 7°C / min, then cool down to 50°C at 120°C / min and keep for 2 min, then increase to 250°C at 3°C / min and keep for 30 min. The cutting times corresponding to the three cutting sections are 1 to 6 min, 6 to 10 min, and 10 to 15 min, respectively. The CO2 cooling valve is opened 1 min before the start of the cutting time period to cool the focusing compound.

[0137] Mass spectrometry conditions: transfer line temperature: 230°C; ionization energy: 70 eV; EI source temperature: 230°C; quadrupole temperature: 150°C; mass scanning range: 33-300 amu.

[0138] The ETS sampling tube was subjected to thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis. The odorist sniffed at the olfactory port and recorded the peak time and odor characteristics of the odor components smelled. At the same time, the compound was qualitatively identified by the mass spectrometry library.

[0139] 4. Analysis of key odor components: The dilution injection effect was achieved by shortening the sampling time of the sampling tube. The sampling times were 30 min, 6 min, 1.2 min, 15 s and 3 s respectively. The obtained sampling tube was analyzed according to step 3.

[0140] The overall smell of menthol cigarette ETS is as follows Figure 8 As shown, the smell is relatively balanced except for the fact that the other smell (mint) is very prominent.

[0141] In order to identify the odor compounds that produce the refreshing odor, the hydrogen flame ionization detector (FID) chromatographic segment that produces the mint odor, i.e. Fig. 9 The segment marked from 4.2 min to 7.5 min is selectively cut into the two-dimensional chromatogram for analysis, which can be done by Fig.10Mass spectrometry analysis and comparison of odor characteristics showed that the odor compound that produces the minty flavor is menthol.

[0142] Comparative Example 1

[0143] The sampling tube sample of the environmental flue gas ETS to be analyzed in Example 1 was measured and analyzed by conventional thermal desorption GC-MS / O, and the chemical components obtained after separation by gas chromatography column were analyzed by GC-MS and olfactory detection port (ODP), wherein the gas chromatography column was a DB-Wax gas chromatography column (60m×0.32mm id×0.25μm). The heating program was: initial temperature 40°C, maintained for 2min, and heated to 200°C at a heating rate of 3°C / min, and maintained for 5min, and then heated to 230°C at 10°C / min, and maintained for 10min.

[0144] The detection conditions of the mass spectrometer are as follows: ionization source energy is 70 eV; ion source temperature is 230°C; transmission line temperature is 235°C; scanning mode is scan; scanning range is 35-300 m / z, and auxiliary heating transmission line (sniffing ODP) temperature is 240°C.

[0145] Will Fig.11 Compared with Example 1 Figure 3 A simple comparison can be made to analyze that the analysis time of the environmental smoke in the comparative example is longer, so that the olfactory identification time is longer. It can be seen from the figure that the separation between the compound chromatographic peaks is poor, which means that there are co-elutions of odors, which will directly interfere with the olfactory identification of the olfactory identification and cause inaccuracy. The accuracy and practical operability of using one-dimensional conventional GC-MS / O to analyze environmental smoke ETS samples are far lower than the determination method in Example 1.

[0146] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A method for analyzing the odor components of environmental smoke, the method comprising the following steps: Overall sniffing of environmental tobacco smoke: Perform a first artificial sniff in a space where environmental tobacco smoke exists to obtain one or more preliminary characteristic smells, and score each of the preliminary characteristic smells; the smell description is selected from a plurality of smells including stinky smell, sour smell, smoked smell, burnt smell, and other smells; the other smells include mint smell, milky smell, and coffee smell; the score is scored on a 7-point scale, and is scored from 1 to 7 according to the smell intensity from weak to strong; Sampling: extracting the ambient tobacco smoke in the space described in step 1), and adsorbing it with an adsorbent to obtain a sample; Characteristic odor component analysis: The sample described in step 2) is subjected to thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis, and combined with the preliminary characteristic taste described in step 1), the peak time and odor characteristics of the characteristic odor components of the ambient smoke smelled are recorded, and the odor compounds are detected by mass spectrometry; the heating program of the first chromatographic column is: 50°C for 2 minutes, then heated to 210°C at a rate of 7°C / min and kept for 10 minutes; the heating program of the second chromatographic column is: cutting section 1: 50°C for 2 minutes, then heated to 78°C at a rate of 7°C / min, then cooled to 50°C at 120°C / min and kept for 2 minutes, then heated to 250°C at 3°C / min and kept for 30 minutes; cutting section 2: 50°C for 2 minutes, then heated to 106°C at a rate of 7°C / min, then cooled to 50°C at 120°C / min and kept for 2 minutes, then heated to 250°C at 3°C / min and kept for 30 minutes; cutting section 3: 50°C for 2 minutes min, then increase the temperature to 141°C at a rate of 7°C / min, then decrease the temperature to 50°C at 120°C / min and hold for 2 min, then increase the temperature to 250°C at 3°C / min and hold for 30 min; cutting section 4: hold at 50°C for 2 min, then increase the temperature to 190°C at a rate of 7°C / min, then decrease the temperature to 50°C at 120°C / min and hold for 2 min, then increase the temperature to 250°C at 3°C / min and hold for 30 min; the cutting times corresponding to the four cutting sections are 1 to 6 min, 6 to 10 min, 10 to 15 min, and 15 to 20 min respectively; Analysis of key odor components: The characteristic odor components of the ambient smoke obtained in step 3) are diluted by shortening the sampling time, and analyzed by the thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis method in step 3). When the characteristic odor components of the ambient smoke cannot be perceived by sniffing, a dilution factor is obtained; the dilution factor is the ratio between the initial sampling time and the shortened sampling time; The environmental smoke odor components include 83 kinds, including 8 olefins, 18 nitrogen heterocyclics, 15 oxygen heterocyclics, 15 phenols, 9 aromatics, 2 amines, 8 acids, and 8 others; the first cutting section odor components include 27 kinds, namely propylene, 1,3-butadiene, isoprene, 2-methylfuran, acrylonitrile, benzene, toluene, trimethylamine, N,N-dimethylethylamine, xylene, pyridine, 2-methylpyridine, styrene, 2-methylpyrazine, 3-methylpyridine, 3-methyl-2-cyclopenten-1-one, 2-cyclopentenone, 5-methyl-2(3H)-furanone, acetic acid, 2-furfural, 2-acetylfuran, pyrrole, propionic acid, butyric acid, acrylic acid, and furfuryl alcohol; In step 2), the sampling time is 5 to 60 min, and the sampling flow rate is 50 to 500 mL / min; In step 3) or step 4), the thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis step includes: first performing thermal desorption, then injecting the sample through a first gas chromatography column for separation, hydrogen flame ionization detector detection, and a second artificial olfactory analysis, and based on the combination of the preliminary characteristic smell in step 1) and the second artificial olfactory analysis, determining the cutting time period of the required characteristic smell; injecting the sample again through the first gas chromatography column for separation, selecting the cutting time period and then further separating through the second gas chromatography column, respectively, and detecting through a mass spectrometer detector and performing a third artificial olfactory analysis to determine the characteristic odor components of the ambient smoke; In step 3) or step 4), the thermal desorption conditions are: the primary thermal desorption temperature is 270-300 °C; The desorption time is 6 to 10 min; The desorption flow rate is 15~100 ml / min; Cold trap adsorption temperature -40~20 ℃; The secondary desorption temperature is 270~300 ℃; the desorption time is 10~15 min; The first chromatographic column is a non-polar chromatographic column, and the second chromatographic column is a polar chromatographic column; the first chromatographic column is selected from SGE-BPX5 gas chromatographic column, Agilent DB-1ms gas chromatographic column, or Agilent DB-5ms gas chromatographic column; the second chromatographic column is selected from Solgel-wax gas chromatographic column, Agilent DB-wax gas chromatographic column, or DB-FFAP gas chromatographic column.

2. The method according to claim 1, characterized in that: In step 2), the adsorbent is selected from one or more of Tenax TA, graphitized carbon black, activated carbon, and molecular sieve.

3. The method according to claim 1, characterized in that: In step 3) or step 4), the mass spectrometry conditions are: Transmission line temperature: 230~250℃; Ionization energy: 65-75eV; EI source temperature: 220~250℃; Quadrupole temperature: 140-150℃; Mass scan range: 33~300 amu.

4. The method according to claim 1, characterized in that: In step 4), the sampling time is 3s~30min, and the sampling flow rate is 50~500 mL / min.

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