CN115389675A - Method for analyzing odor components of environmental smoke - Google Patents
Method for analyzing odor components of environmental smoke Download PDFInfo
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- CN115389675A CN115389675A CN202211073401.0A CN202211073401A CN115389675A CN 115389675 A CN115389675 A CN 115389675A CN 202211073401 A CN202211073401 A CN 202211073401A CN 115389675 A CN115389675 A CN 115389675A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
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Abstract
The application relates to the technical field of analysis of chemical components in environmental smoke, in particular to an analysis method of odor components of the environmental smoke. The method comprises the following steps: 1) Integrally smelling environmental tobacco smoke; 2) Sampling; 3) Analyzing characteristic odor components: 4) And (4) analyzing key odor components. The method can realize the enrichment of low-concentration odor compounds, directly performs thermal desorption analysis after sampling without complex pretreatment, is simple, convenient and quick, has good repeatability and high sensitivity, and can completely meet the analysis requirement of odor components in environmental smoke; by diluting the sampling sample, key odor substances can be determined, and accurate identification of odor components in environmental smoke is realized; the method is more suitable for odor analysis of complex samples, can purposefully cut concerned odor characteristics, effectively removes interference of odorless compounds or compounds with light odor but high content, and has better selectivity and efficiency.
Description
Technical Field
The application relates to the technical field of analysis of chemical components in environmental smoke, in particular to an analysis method of odor components of the environmental smoke.
Background
Environmental Tobaco Smoke (ETS) is a complex chemical mixture produced by the combustion of Tobacco products, originating from the sidestream Smoke (75%) produced when the Tobacco products are combusted and the mainstream Smoke (15%) exhaled by the smoker, which is highly diluted and aged with air to form ETS. Research shows that ETS is an important air quality pollution source and has certain harmfulness to human health, and the research of ETS on environmental pollution mainly focuses on qualitative and quantitative analysis of chemical components at present.
The odor components in the ETS are substance components which can be directly felt by human beings and are closely related to the air quality, and the research on the odor components in the ETS has very important significance for correctly recognizing and evaluating the environmental odor pollution caused by the environmental smoke, however, the research on the odor components in the ETS is rarely reported at present.
Odor studies have generally focused on food, tobacco, flavors and fragrances, and environmental monitoring using gas chromatography-mass spectrometry/sniffing (GC-MS/O) technology, which combines precision instrumental analysis with human sensitive olfaction to identify odor actives.
The environmental smoke has complex components and low content of highly diluted compounds (ug/m) 3 Grade), if the conventional one-dimensional GC-MS/O instrument sold in the market is adopted for analysis, the chromatographic analysis capability is limited due to the fact that only a single-polarity analysis column is provided, so that the separation effect of odor compounds is poor, the phenomenon of odor co-outflow exists, and the odor analysis requirements of ETS species of environmental smoke cannot be met. However, if a two-dimensional GC-MS/O instrument is adopted for analysis, although the analysis capability of the instrument is improved, the instrument sample injection mode is Solid Phase Microextraction (SPME) or solvent extraction, the sensitivity is limited by the extraction capacity, the selective adsorption of an extraction head and the sample injection amount, the effective analysis of the environmental smoke odor components cannot be realized, and related research reports about the ETS odor component analysis do not exist at present
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide an analysis method for odor components of environmental tobacco smoke, which is used for solving the problems in the prior art that the odor components of environmental tobacco smoke are low in analysis sensitivity by using instruments and cannot be effectively analyzed.
To achieve the above and other related objects, the present application provides, in one aspect, a method for analyzing an odor component of environmental smoke, the method including the steps of:
1) Integral smell of environmental tobacco smoke: carrying out first artificial smell in a space with environmental tobacco smoke to obtain one or more preliminary characteristic tastes, and grading each preliminary characteristic taste;
2) Sampling: extracting the environmental tobacco smoke in the space in the step 1), and adsorbing the environmental tobacco smoke by using an adsorbent to obtain a sample;
3) Analyzing characteristic odor components: carrying out thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis on the sample in the step 2), recording the peak time and the smell characteristics of the characteristic smell components of the environmental smoke sniffed by combining the primary characteristic taste in the step 1), and simultaneously detecting the smell compounds by mass spectrometry;
4) Analysis of key odor components: diluting the characteristic odor components of the environmental smoke obtained in the step 3) by shortening the sampling time, analyzing by adopting the thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis method of the step 3), and obtaining a dilution factor when the characteristic odor components of the environmental smoke cannot be sensed by sniffing.
The application provides an environmental flue gas odor component analysis device on the other hand, which comprises a sampling pipe, a cold trap, a first chromatographic column, a second chromatographic column and a mass spectrum detector which are communicated in sequence; the sampling pipe and the cold trap are arranged in a thermal desorption instrument; the first chromatographic column and the second chromatographic column are arranged in the column incubator; a communication pipeline between the first chromatographic column and the second chromatographic column is also provided with CO 2 A cooling valve; the smell distinguishing port is communicated with the first chromatographic column and the second chromatographic column respectively; the hydrogen flame ion detector is connected with the first chromatographic column.
The application further provides the application of the environmental smoke odor component analysis device in environmental smoke odor analysis.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the method, the sampling pipe with the adsorbent is adopted to adsorb and enrich the odor components of the environmental smoke so as to improve the analysis concentration of the odor compounds and realize the enrichment of low-concentration odor compounds; after sampling, the sampling tube directly performs thermal desorption analysis without complex pretreatment, and the method is simple, convenient and quick, has good repeatability and high sensitivity, and can completely meet the analysis requirement of the odor components in the environmental flue gas.
2. The multidimensional gas chromatography-mass spectrometry that this application was built smells the device, through the cooling focus of two different polarity chromatographic columns of series connection and carbon dioxide, promotes the separation ability and the detectivity of instrument, is equipped with three kinds of detectors, including hydrogen flame ion detector, mass spectrum detector, people's nose, smells and distinguishes mouthful nothing and flows out altogether, makes the odor compound in the complicated environment flue gas can obtain the abundant separation, realizes the accurate of smelling the gas composition in the environment flue gas.
3. The sampling time is changed to achieve the dilution effect on the sampling sample, and the dilution factor is determined through smelling, so that the key odor substance can be determined, the key odor substance is an important component of the odor pollution caused by the environmental smoke, and the accurate analysis and judgment of the odor pollution caused by the environmental smoke are realized.
4. Compared with a one-dimensional gas chromatography-mass spectrometry sniffing analysis technology, the method has better analysis effect on complex matrix samples, is more suitable for the odor analysis of the complex samples, and can purposefully cut concerned odor characteristics, such as mint type cigarettes and milk flavor type cigarettes in the analysis of the environmental smoke of the outer flavor type cigarettes; the interference of compounds which are odorless or have light odor but high content such as nicotine in the environmental smoke can be effectively removed, the method has the advantages of better selectivity and high efficiency, effectively avoids the smell of a sniffer for a long time, and realizes the enrichment and qualitative detection of odorous and trace components.
Drawings
Fig. 1 is a schematic diagram of an environmental smoke odor component analysis device.
FIG. 2 shows the radar chart of the overall sensory smell evaluation of the environmental smoke of domestic cigarettes.
FIG. 3 shows the mass spectrum of the first cut segment of smoke in domestic cigarette environment.
FIG. 4 shows the mass spectrogram of the second cut segment of the smoke in the domestic cigarette environment.
Figure 5 shows the radar chart of the overall sensory smell evaluation of the environmental smoke of the blended cigarette.
FIG. 6 shows a mass spectrum of the first cut segment of the environmental smoke of the blended cigarette.
FIG. 7 shows a second cut segment mass spectrum of the environmental smoke of the blended cigarette.
Figure 8 shows an overall sensory sniff evaluation radar plot of ambient smoke for a mint-type cigarette.
Figure 9 shows a chromatogram of a hydrogen flame ion detector for a mint-type cigarette portion.
Figure 10 shows the cut segment mass spectra that produce a mint flavor for a mint-type cigarette.
FIG. 11 shows a mass spectrum obtained by conventional GC-MS detection of an environmental flue gas sample in comparative example 1 of the present invention.
Element number description:
1. thermal desorption instrument
11. Cold trap
12. Sampling tube
2. Column oven
21. First gas chromatography column
211. Sample introduction end of first gas chromatography column
212. Sample outlet end of first gas chromatographic column
22. Second gas chromatography column
221. Sample introduction end of second gas chromatography column
222. Sample outlet end of second gas chromatographic column
23 CO 2 Cooling valve
3. Hydrogen flame ion detector
4. Mass spectrum detector
5. Mouth differentiation by sniffing
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention is further described with reference to the following embodiments. It should be understood that the examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures used in the following examples are conventional and, unless otherwise indicated, other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein.
The inventor of the invention discovers a method for analyzing odor components in environmental smoke based on a thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing technology through a great deal of research and research, establishes a thermal desorption-multidimensional gas chromatography-mass spectrometry analysis method for the odor components in the environmental smoke for the first time by establishing a thermal desorption and multidimensional gas chromatography-mass spectrometry sniffing combined system so as to meet the analysis requirement of the odor components in the environmental smoke, and completes the invention on the basis.
The application provides an analysis method of environmental smoke odor components, which comprises the following steps:
1) Integral smell of environmental tobacco smoke: carrying out first artificial smell in a space with environmental tobacco smoke to obtain one or more preliminary characteristic tastes, and grading each preliminary characteristic taste;
2) Sampling: extracting the environmental tobacco smoke in the space in the step 1), and adsorbing the environmental tobacco smoke by using an adsorbent to obtain a sample;
3) Analyzing characteristic odor components: carrying out thermal desorption-multidimensional gas chromatography-mass spectrometry olfactory analysis on the sample in the step 2), recording the peak time and odor characteristics of the smelly environmental smoke characteristic odor component by combining the preliminary characteristic taste in the step 1), and simultaneously detecting an odor compound by mass spectrometry;
4) Analysis of key odor components: diluting the characteristic odor components of the environmental smoke obtained in the step 3) by shortening the sampling time, analyzing by adopting the thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis method of the step 3), and obtaining a dilution factor when the characteristic odor components of the environmental smoke cannot be sensed by sniffing.
In the analysis method of the environmental smoke odor component provided by the application, the step 1) is the integral smell of the environmental tobacco smoke: performing a first artificial sniffing in a space where ambient tobacco smoke is present, obtaining one or more preliminary characteristic tastes, and scoring each of said preliminary characteristic tastes. The smell is conventionally used in the tobacco field and is identified through artificial sensory smell at an olfactory mouth, namely, the smell components of the environmental smoke are subjected to olfactory analysis by an olfactory operator with good olfactory perception and healthy body. The odor description includes a variety of off-flavors, sour flavors, smoke flavors, burnt flavors, and others. Such other flavors include minty, milk flavor, coffee flavor, and the like. The score may be a multiple score, preferably a 7-score, with scores ranging from 1 to 7 being performed from weak to strong odor intensity.
In the analysis method of the environmental smoke odor component provided by the application, the step 2) is sampling: extracting the environmental tobacco smoke in the space in the step 1), and adsorbing the environmental tobacco smoke by using an adsorbent to obtain a sample. The sampling may be by means of an air sampling device, preferably an air sampling pump, for example. The sampling tube is made of a glass material, and the adsorbent is selected from one or more of Tenax TA, graphitized carbon black, activated carbon and molecular sieves. Preferably, the adsorbent type is Tenax TA. The sampling tube with the adsorbent is used for sampling, so that the environmental smoke can be conveniently trapped and adsorbed, the analysis concentration of the odor compounds is improved, the low-concentration odor compounds are enriched, the environmental smoke sample can be obtained in the environment with low concentration, and the subsequent analysis is convenient.
In step 2) of the present application, the sampling time is 5 to 60min, preferably 5 to 30min, 30 to 50min, or 50 to 60 min. The sampling flow rate is 50-500 mL/min, preferably 50-200 mL/min, 200-400 mL/min, 400-500 mL/min, etc. Preferably, the sampling time is 30min and the sampling flow rate is 200ml/min.
In the analysis method of the environmental smoke odor components, step 3) is characteristic odor component analysis: carrying out thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis on the sample in the step 2), recording the peak time and the smell characteristics of the characteristic smell components of the environmental smoke sniffed by combining the preliminary characteristic smell in the step 1), and simultaneously detecting the smell compounds by mass spectrometry. Step 4) is key odor component analysis: diluting the characteristic odor components of the environmental smoke obtained in the step 3) by shortening the sampling time, analyzing by adopting the thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis method of the step 3), and obtaining a dilution factor when the characteristic odor components of the environmental smoke cannot be sensed by sniffing.
In a specific embodiment of the present application, the thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis step comprises: carrying out thermal desorption, then separating the sample by a first gas chromatographic column, detecting by a hydrogen flame ion detector and carrying out secondary artificial smell analysis, and determining the cutting time period of the required characteristic taste based on the combination of the primary characteristic taste and the secondary artificial smell in the step 1); and after the sample is injected again and is separated by the first gas chromatographic column, selecting a cutting time period and then separating by the second gas chromatographic column, and respectively detecting by a mass spectrum detector and carrying out third manual smell analysis to determine the characteristic odor components of the environmental smoke.
In a specific embodiment of the present application, the multi-dimensional gas chromatography employs two gas chromatography columns, the first column being a non-polar column and the second column being a polar column. Preferably, the first chromatographic column is selected from the group consisting of an SGE-BPX5 gas chromatographic column or an Agilent DB-1ms gas chromatographic column or an Aglient DB-5ms gas chromatographic column; the second chromatographic column is selected from a Solgel-wax gas chromatographic column or an Agilent DB-wax gas chromatographic column or a DB-FFAP gas chromatographic column.
In step 3) or step 4), the thermal desorption conditions are as follows:
the first-stage thermal desorption temperature is 270-300 ℃; preferably 270 to 280 ℃, 280 to 290 ℃, 290 to 300 ℃ and the like.
The desorption time is 6-10 min; preferably 6 to 8min, 8 to 10min, etc.
The desorption flow is 15-100 ml/min; preferably 15-20 ml/min, 20-50 ml/min, 50-100 ml/min and the like.
The adsorption temperature of the cold trap is minus 40 to 20 ℃; preferably-40 to-20 ℃, 20 to 10 ℃,10 to 20 ℃ and the like.
The secondary desorption temperature is 270-300 ℃; preferably 270 to 280 ℃, 280 to 290 ℃, 290 to 300 ℃ and the like.
The desorption time is 10-15 min; preferably 10 to 12min, 12 to 15min, etc.
Preferably, the thermal desorption conditions are:
the first-stage thermal desorption temperature is 280 ℃, and the desorption time is 10min;
the desorption flow is 20ml/min;
the secondary desorption temperature is 300 ℃, and the desorption time is 15min.
In step 3) or step 4), the temperature raising program of the first chromatographic column is as follows: keeping the temperature at 40-60 ℃ for 1-5 min, then raising the temperature to 200-230 ℃ at the speed of 2-10 ℃/min, and keeping the temperature for 5-20 min.
In step 3) or step 4), the temperature raising program of the second chromatographic column is as follows: keeping the temperature at 40-50 ℃ for 1-5 min, then increasing the temperature to the temperature required by the cutting time period at the speed of 4-8 ℃/min, then reducing the temperature to 40-50 ℃ at the cooling speed of 20-120 ℃/min, keeping the temperature for 1-5 min, and increasing the temperature to 230-250 ℃ at the speed of 2-7 ℃/min, and keeping the temperature for 10-30 min.
In a specific embodiment of the present application, the cutting time period is determined as a retention time period in a gas chromatogram obtained by detecting a corresponding component by a hydrogen flame ion detector corresponding to the odor component to be detected determined by sniff analysis. And the cutting time period is selected to set the retention time between peak valleys in the gas chromatogram as the cutting time period, wherein in the area with fewer chromatographic peaks and lower content, a wider cutting time period is set, and conversely, a narrower cutting time period is set.
In step 3) or step 4) of the present application, the mass spectrometry conditions are:
transmission line temperature: 230 to 250 ℃; preferably 230 to 240 ℃ and 240 to 250 ℃.
Ionization energy: 65-75eV; preferably 65-70eV, 70-75eV, or the like.
EI source temperature: 220 to 250 ℃; preferably 220 to 230 ℃, 230 to 240 ℃, 240 to 250 ℃ and the like.
Temperature of the quadrupole rods: 140-150 ℃; preferably 140-142 deg.C, 142-145 deg.C, 145-150 deg.C, etc.
Mass scan range: 33-300 amu; preferably 33 to 66amu, 66 to 100amu, 100 to 200amu, 200 to 300amu, and the like.
The qualitative mode of mass spectrum is selected from one or two of NIST mass spectrum library retrieval compound structural formula qualitative mode and Wiely mass spectrum library retrieval compound structural formula qualitative mode.
Preferably, the mass spectrometry conditions are:
transmission line temperature: 240 ℃;
ionization energy: 70eV;
EI source temperature: 240 ℃;
temperature of the quadrupole rods: 150 ℃;
mass scan range: 33 to 300amu.
In step 3) or step 4) of the present application, the sniff analysis is used to record the time-to-peak and odor characteristics of the odor component.
In the step 4), the sampling time is 3s to 30min, preferably 3s to 15s, 15s to 60s, 1 to 1.2min, 1.2min to 6min, 6min to 30min and the like. The sampling flow rate is 50-500 mL/min, preferably 50-500 mL/min, 50-200 mL/min, 200-400 mL/min, 400-500 mL/min and the like. Preferably, the sampling times for dilution analysis are 30min, 6min, 1.2min, 15s and 3s, respectively. And obtaining a dilution factor according to the ratio of the initial sampling time to the shortened sampling time, wherein the dilution factor is a dilution factor. Specifically, when the initial sampling time is 30min and the shortened sampling time is 6min, the dilution factor is 5. The greater the dilution factor, the greater the overall odor contribution of the compound to the ambient smoke. The sampling time is changed to achieve the dilution effect on the sampling sample, the dilution factor is determined through sniffing, the key odor substance can be determined, the key odor substance is an important component causing odor pollution to the environmental smoke, no co-outflow matter exists at the sniffing port, and the accurate identification of the odor component in the environmental smoke is realized.
The application also provides an environmental smoke odor component analysis device, as shown in fig. 1, which comprises 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 sequentially communicated; the sampling pipe 12 and the cold trap 11 are arranged in the thermal desorption instrument 1; the first chromatographic column 21 and the second chromatographic column 22 are arranged in the column incubator 2; the communication device between the first chromatographic column 21 and the second chromatographic column 22 is also provided with CO 2 A cooling valve 23; the device further comprises an olfactory discrimination port 5, wherein the olfactory discrimination port 5 is respectively connected with the first chromatographic column 21 and the second chromatographic column 22; the device also comprises a hydrogen flame ion detector 3, wherein the hydrogen flame ion detector 3 is connected with the first chromatographic column 21. Through the cooling focusing of two different polarity chromatographic columns and carbon dioxide of series connection, promote the separation ability and the detectivity of instrument, be equipped with three kinds of detectors, including hydrogen flame ion detector, mass spectrum detector, people's nose, make the smell compound in the complicated environment flue gas obtain fully separating.
In the specific embodiment of the present application, the cold trap 11 is in communication with the first chromatography column 21 through the sample inlet end 211 of the first chromatography column. The hydrogen flame ion detector 3 and the sniffing port 5 are both communicated with the first chromatographic column 21 through the sample outlet end 212 of the first chromatographic column. The sample outlet end 212 of the first chromatographic column is communicated with the second chromatographic column 22 through the sample inlet end 221 of the second chromatographic column. The mass spectrometer 4 and the sniffing port 5 are both communicated with the second chromatographic column 22 through the sample outlet end 222 of the second chromatographic column.
In the embodiment of this application, thermal desorption instrument 1 can realize adsorbing and thermal desorption to the environment flue gas, and is specific, through adsorbent in the sampling pipe 12 adsorbs the environment flue gas, then through the desorption that heaies up earlier, the rethread the cold-trap 11 cooling is adsorbed, and the desorption that heaies up again to be convenient for carry out the analysis of smell composition to the lower environment flue gas of concentration.
In the specific embodiment of the present application, the column oven 2 can perform multidimensional gas chromatography analysis on the environmental smoke odor component after thermal desorption, first obtain a cutting time period by the hydrogen flame ion detector 3 and the sniffing port 5 through a one-dimensional procedure, then obtain a peak image of the specific environmental smoke odor component by the mass spectrometer 4 and the sniffing port 5 according to a two-dimensional procedure after the cutting time period, and obtain a characteristic analysis and a corresponding compound for the environmental smoke odor component by combining the aforementioned overall sniffing of the environmental smoke. Compared with a one-dimensional gas chromatography-mass spectrometry olfactometry analysis technology, the method has better analysis effect on a complex matrix sample, is more suitable for odor analysis of the complex sample, can purposefully cut concerned odor characteristics, effectively removes interference of compounds which have no odor or light odor but higher content in environmental smoke, such as nicotine, has better selectivity and high efficiency, effectively avoids olfactors from smelling for a longer time, and realizes enrichment and qualitative detection of odorous and trace components.
In a specific embodiment of the present application, the CO 2 The cooling valves 23 are opened 1-5 min before the start of the cutting period and closed before the next temperature rise, respectively, for cooling the focusing compound.
The application also provides the application of the environmental smoke odor component analysis device in environmental smoke odor analysis. When the environmental smoke exists, the method can be used for analyzing the odor in the environmental smoke, so that the rational index for evaluating the environmental smoke is obtained.
As described above, the present application provides an analysis method for odor components of environmental smoke, wherein a sniffer performs overall sniffing evaluation on the environmental smoke, the environmental smoke is sampled and enriched by a sampling tube, and a thermal desorption and multidimensional gas chromatography-mass spectrometry sniffing combined technology is adopted to develop an analysis method for the odor components in the environmental smoke for the first time, so that the odor characteristic analysis of the odor components in the environmental smoke is realized, and the key odor components affecting the environmental smoke are determined. The method for measuring the total components of the odor components in the environmental smoke is established for the first time.
The invention provides an analysis method of environmental smoke odor components, which comprises the following steps:
1. a sampling pipe with an adsorbent is adopted to adsorb and enrich the odor components of the environmental smoke so as to improve the analysis concentration of the odor compounds and realize the enrichment of the low-concentration odor compounds. After sampling, the sampling tube directly performs thermal desorption analysis without complex pretreatment, and the method is simple, convenient and rapid, has good repeatability and high sensitivity, and can completely meet the analysis requirement of the odor components in the environmental smoke.
2. The multidimensional gas chromatography-mass spectrometry sniffing device is characterized in that two chromatographic columns with different polarities and carbon dioxide are connected in series to cool and focus, so that the separation capacity and detection sensitivity of the instrument are improved, three detectors are arranged and comprise a hydrogen flame ion detector, a mass spectrometry detector and a human nose, no co-outflow substance exists in sniffing and distinguishing mouths, odor compounds in complex environment smoke can be fully separated, and accurate distinguishing of odor components in the environment smoke is realized.
3. The sampling time is changed to achieve the dilution effect on the sampling sample, and the dilution factor is determined through smelling, so that the key odor substance can be determined, the key odor substance is an important component of the odor pollution caused by the environmental smoke, and the accurate analysis and judgment of the odor pollution caused by the environmental smoke are realized.
4. Compared with a one-dimensional gas chromatography-mass spectrometry olfactory analysis technology, the method has better analysis effect on complex matrix samples, is more suitable for the odor analysis of complex samples, and can purposefully cut concerned odor characteristics, such as mint type cigarettes and milk flavor type cigarettes in the analysis of environmental smoke of the outer flavor type cigarettes; the interference of compounds which are odorless or have light odor but high content such as nicotine in the environmental smoke can be effectively removed, the method has the advantages of better selectivity and high efficiency, effectively avoids the smell of a sniffer for a long time, and realizes the enrichment and qualitative detection of odorous and trace components.
The invention of the present application is further illustrated by the following examples, which are not intended to limit the scope of the present application.
The materials and equipment used in the following examples are as follows:
materials: tenax TA, carbotrap, activated carbon glass sampling tube (1/4 inch diameter, 3.5 inches in length, supelco, USA). Finished cigarettes (including domestic flue-cured tobacco, foreign flue-cured tobacco, blended cigarettes and mint cigarettes) are all commercially available.
The instrument comprises: turboMatrix ATD thermal desorption apparatus (Perkin Elmer, USA); 7890B/5977A GC-MS (Agilent, USA); CDS Model 9600 sampling tube burn-in apparatus (CDS Analytical, USA); SIAA-CYY-2 two-channel gas sampling instrument (Shanghai' an spectral experiment science and technology Co., ltd.).
Example 1
1. Integral smell of environmental smoke:
the method comprises the steps of placing a domestic flue-cured tobacco in a simulated environment flue gas cabin of 40cm multiplied by 23cm multiplied by 24cm, carrying out smoldering under a static non-ventilation condition, opening a fan for 2min after smoldering is finished to form ETS, smelling gas in the space of the environment flue gas cabin containing the ETS by a sniffer, describing sensed smell characteristics, and grading the strength of each characteristic smell in a seven-point system.
2. The sampling pipe enriches the odor components of the environmental smoke:
and after the integral sniffing is finished, connecting one end of a sampling tube containing the Tenax TA adsorbent with an air sampling pump, extracting air at the flow rate of 200ml/min for 30min, and collecting ETS. After sampling is finished, the Teflon covers are tightly covered at the two ends of the sampling tube, and the sample is stored at room temperature to be analyzed.
3. Analyzing characteristic odor components:
thermal desorption instrument conditions: carrier gas: helium (more than or equal to 99.999%); first-stage desorption temperature: 270 ℃; first-stage desorption time: 10min; the desorption flow is 20ml/min; cold trap adsorption temperature: -40 ℃; secondary desorption temperature: 300 ℃; secondary desorption time: 10min;
gas chromatography conditions: a first chromatographic column: BPX5 capillary column (30 m.times.0.53 mm.times.0.5 μm); a second chromatographic column: solgel-wax capillary column (30 m.times.0.53 mm. Times.0.5 μm); carrier gas: helium (more than or equal to 99.999%); chromatographic temperature raising procedure. One-dimensional analysis: keeping the temperature at 50 ℃ for 2min, then heating to 210 ℃ at the speed of 7 ℃/min, and keeping the temperature for 10min. Two-dimensional analysis: cutting section 1: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 78 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at the speed of 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at the speed of 3 ℃/min for 30min. And (3) cutting the section 2: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 106 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. Cutting section 3: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 141 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. Cutting section 4: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 190 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. The cutting time of the four cutting sections is 1-6 min, 6-10min, 10-15min and 15-20 min respectively. CO 2 2 The cooling valves were opened 1min before the start of the cutting period, respectively, for cooling the focusing compound.
Mass spectrum conditions: transmission line temperature: 230 ℃; ionization energy: 70eV; EI source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; mass scan range: 33-300 amu.
And (3) carrying out thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis on the ETS sampling tube, sniffing by a sniffer at a sniffing mouth, recording the peak appearance time and the odor characteristics of the sniffed odor components, and simultaneously carrying out qualitative analysis on the compound by a mass spectrum library.
4. Analysis of key odor components:
and (4) achieving the dilution sampling effect by shortening the sampling time of the sampling tube, wherein the sampling time is respectively 30min, 6min, 1.2min, 15s and 3s, and analyzing the obtained sampling tube according to the step (3).
The integral smell of domestic flue-cured tobacco ETS is shown in figure 2, and the smell, odor and smoke smell of the burnt tobacco ETS are obvious.
And qualitatively analyzing the retrieval result by adopting mass spectrum database retrieval, wherein the mass spectrum database is an NIST database, the component judgment is based on that the selection matching degree is more than or equal to 85, and 83 odor components are determined according to the odor characteristics of domestic cigarettes, wherein 8 types of olefins, 18 types of nitrogen heterocycles, 15 types of oxygen heterocycles, 15 types of phenols, 9 types of aromatics, 2 types of amines, 8 types of acids and 8 types of others are combined with the characteristic odor components of smells. Different compounds have different odor characteristics, such as trimethylamine (amine odor, fishy odor), 2-methylpyrazine (chocolate, sweet odor), isovaleric acid (rancid, sour odor), m-cresol (smoke odor, medicinal odor), maltol (caramel, nut odor), and the like. The odor characteristics and dilution factor of the odorous compounds of the first cut segment shown in table 1 were found as a dilution factor from the ratio between the initial sampling time and the shortened sampling time. Specifically, when the initial sampling time is 30min and the shortened sampling time is 6min, the dilution factor is 5. A greater dilution factor indicates a greater overall odor contribution of the compound to the ambient smoke. Compounds with a high dilution factor are key odor components, such as trimethylamine, 3-methyl-2-cyclopenten-1-one, 2-acetylfuran, and the like. FIG. 3 shows a first cut mass spectrum. Figure 4 shows the mass spectrum of the second cut segment.
TABLE 1 odor components of the first cut segment in the cigarette environmental smoke in China, odor characteristics thereof and dilution factor thereof
Example 2
1. Integral smell of environmental smoke:
placing a mixed cigarette in a simulated environment smoke cabin of 40cm multiplied by 23cm multiplied by 24cm, carrying out smoldering under the static non-ventilation condition, opening a fan for 2min after smoldering is finished to form ETS, smelling the gas in the environment smoke cabin containing the ETS by a sniffer, describing the sensed smell characteristics, and grading the strength of each characteristic smell by seven grades.
2. The sampling tube enriches the environmental smoke odor components: and after the integral sniffing is finished, connecting one end of a sampling tube containing the Tenax TA adsorbent with an air sampling pump, extracting air at the flow rate of 200ml/min for 30min, and collecting ETS. After sampling is finished, the Teflon covers are tightly covered at the two ends of the sampling tube, and the sample is stored at room temperature to be analyzed.
3. Analyzing characteristic odor components: thermal desorption instrument conditions: carrier gas: helium (more than or equal to 99.999%); first-order desorption temperature: 270 ℃; first-stage desorption time: 10min; the desorption flow is 20ml/min; cold trap adsorption temperature: -40 ℃; secondary desorption temperature: 300 ℃; secondary desorption time: 10min;
gas chromatography conditions: a first chromatographic column: BPX5 capillary column (30 m.times.0.53 mm.times.0.5 μm); second chromatographic column: solgel-wax capillary column (30 m.times.0.53 mm. Times.0.5 μm); carrier gas: helium (more than or equal to 99.999%); and (4) chromatographic temperature raising program. One-dimensional analysis: keeping the temperature at 50 ℃ for 2min, then heating to 220 ℃ at the speed of 7 ℃/min, and keeping the temperature for 20min. Two-dimensional analysis: cutting section 1: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 78 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at the speed of 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at the speed of 3 ℃/min for 30min. And (3) cutting the section 2: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 106 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. Cutting section 3: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 141 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. And (4) cutting section: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 190 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. The cutting time of the four cutting sections is 1-6 min, 6-10 min, 10-10 min, 15-20 min, CO respectively 2 The cooling valves were opened 1min before the start of the cutting period, respectively, for cooling the focusing compound.
Mass spectrum conditions: transmission line temperature: 230 ℃; ionization energy: 70eV; EI source temperature: 230 ℃; temperature of the quadrupole rods: 150 ℃; mass scan range: 33-300 amu.
And (3) carrying out thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis on the ETS sampling tube, sniffing by a sniffer at a sniffing mouth, recording the peak appearance time and the odor characteristics of the sniffed odor components, and simultaneously carrying out qualitative analysis on the compound by a mass spectrum library.
4. Analysis of key odor components: and (3) the sampling time of the sampling tube is shortened to achieve the dilution sampling effect, the sampling time is respectively 30min, 6min, 1.2min, 15s and 3s, and the obtained sampling tube is analyzed according to the step (3).
The whole smell of the mixed type cigarette ETS is shown in figure 5, the whole smell intensity is high, the odor and the burnt odor are very prominent, and the smoking taste is inferior.
And qualitatively analyzing the retrieval result by adopting mass spectrum database retrieval, wherein the mass spectrum database is an NIST database, the component judgment is based on that the selection matching degree is more than or equal to 85, and 83 odor components are determined according to the characteristic odor components of the blended type cigarette by combining the smelly odor characteristics, wherein 8 types of olefins, 18 types of nitrogen heterocycles, 15 types of oxygen heterocycles, 15 types of phenols, 9 types of aromatics, 2 types of amines, 8 types of acids and 8 types of others are included. The mass spectrum of the first cut segment of the mixed cigarette ETS is shown in figure 6. The mass spectrum of the ETS second cut segment of the blended cigarette is shown in figure 7.
Example 3
1. Integral smell of environmental smoke:
a mint type cigarette is placed in a simulated environment smoke cabin of 40cm multiplied by 23cm multiplied by 24cm, smoldering is carried out under the static non-ventilation condition, a fan is turned on for 2min after smoldering is finished, ETS is formed, a sniffer smells the gas in the space of the environment smoke cabin containing the ETS, the sensed smell characteristics are described, and seven-point grading is carried out on the strength of each characteristic smell.
2. The sampling pipe enriches the odor components of the environmental smoke: and after the integral sniffing is finished, connecting one end of a sampling tube containing the Tenax TA adsorbent with an air sampling pump, extracting air at the flow rate of 200ml/min for 30min, and collecting ETS. After sampling is finished, the Teflon covers are tightly covered at the two ends of the sampling tube, and the sample is stored at room temperature to be analyzed.
3. Analyzing characteristic odor components: thermal desorption instrument conditions: carrier gas: helium (more than or equal to 99.999%); first-order desorption temperature: 270 ℃; first-stage desorption time: 10min; the desorption flow is 20ml/min; cold trap adsorption temperature: -40 ℃; secondary desorption temperature: 300 ℃; secondary desorption time: 10min;
gas chromatography conditions: a first chromatographic column: BPX5 capillary column (30 m.times.0.53 mm.times.0.5 μm); second chromatographic column: solgel-wax capillary column (30 m.times.0.53 mm. Times.0.5 μm); carrier gas: helium (more than or equal to 99.999%); chromatographic temperature raising procedure. One-dimensional analysis: keeping the temperature at 50 ℃ for 2min, then heating to 200 ℃ at the speed of 7 ℃/min, and keeping the temperature for 5min. Two-dimensional analysis: cutting section 1: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 78 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. And (3) cutting the section 2: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 106 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. Cutting section 3: keeping the temperature at 50 ℃ for 2min, then increasing the temperature to 141 ℃ at the speed of 7 ℃/min, then reducing the temperature to 50 ℃ at 120 ℃/min for 2min, and then increasing the temperature to 250 ℃ at 3 ℃/min for 30min. The cutting time of the three cutting sections is 1-6 min, 6-10min, 10-15min respectively 2 The cooling valves were opened 1min before the start of the cutting period, respectively, for cooling the focusing compound.
Mass spectrum conditions: transmission line temperature: 230 ℃; ionization energy: 70eV; EI source temperature: 230 ℃; quadrupole rod temperature: 150 ℃; mass scan range: 33-300 amu.
And (3) carrying out thermal desorption-multidimensional gas chromatography-mass spectrum sniffing analysis on the ETS sampling tube, sniffing by a sniffer at the sniffing mouth, recording the peak time and the odor characteristics of the sniffed odor components, and simultaneously carrying out qualitative analysis on the compound by a mass spectrum library.
4. Analysis of key odor components: and (3) the sampling time of the sampling tube is shortened to achieve the dilution sampling effect, the sampling time is respectively 30min, 6min, 1.2min, 15s and 3s, and the obtained sampling tube is analyzed according to the step (3).
The overall smell of the ETS of the mint-type cigarette is shown in fig. 8, and the smell is relatively balanced except that other flavors (mint flavor) are very prominent.
To identify the compound that produces a cooling odor, the mint odor-producing hydrogen Flame Ionization Detector (FID) spectrum, labeled 4.2min to 7.5min as shown in fig. 9, was selectively cut alone into two-dimensional chromatograms for analysis, which were mass-spectrometrically analyzed and compared for odor characteristics in fig. 10, showing that the mint-producing odor compound was menthol.
Comparative example 1
The sample tube for collecting the environmental flue gas ETS to be analyzed in example 1 was subjected to measurement and analysis using a conventional thermal desorption GC-MS/O, and the chemical components obtained after separation by a gas chromatography column, which is a DB-Wax gas chromatography column (60 m × 0.32mm id × 0.25 μm), were analyzed by GC-MS and an Olfactory Diagnostic Port (ODP). The temperature rising procedure is as follows: the initial temperature is 40 ℃, the temperature is kept for 2min, the temperature is increased to 200 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 5min, the temperature is increased to 230 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 10min.
The detection conditions of the mass spectrum detector are as follows: the ionization source energy is 70eV; the ion source temperature is 230 ℃; the transmission line temperature is 235 ℃; the scanning mode is scan; the scanning range is 35-300 m/z, and the temperature of the auxiliary heating transmission line (sniffing ODP) is 240 ℃.
As can be analyzed by simply comparing fig. 11 with fig. 3 in example 1, the analysis time for analyzing the environmental smoke in the comparative example is longer, so that the sniffing time of the sniffer is longer, and it can be seen from the figure that the separation degree between the compound chromatographic peaks is poorer, so that a co-effluent of odor exists, which directly interferes with the sniffing of the sniffer, and inaccuracy exists. The accuracy and practical operability of analyzing environmental flue gas ETS samples by adopting one-dimensional conventional GC-MS/O are far lower than those of the determination method in the embodiment 1.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for analyzing the odor components of environmental smoke, comprising the following steps:
1) Integral smell of environmental tobacco smoke: carrying out first artificial smell in a space with environmental tobacco smoke to obtain one or more preliminary characteristic tastes, and grading each preliminary characteristic taste;
2) Sampling: extracting the environmental tobacco smoke in the space in the step 1), and adsorbing the environmental tobacco smoke by using an adsorbent to obtain a sample;
3) Analyzing characteristic odor components: carrying out thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis on the sample in the step 2), recording the peak time and the smell characteristics of the characteristic smell components of the environmental smoke sniffed by combining the primary characteristic taste in the step 1), and simultaneously detecting the smell compounds by mass spectrometry;
4) Analysis of key odor components: diluting the characteristic odor components of the environmental smoke obtained in the step 3) by shortening the sampling time, analyzing by adopting the thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis method of the step 3), and obtaining a dilution factor when the characteristic odor components of the environmental smoke cannot be sensed by sniffing.
2. The method of claim 1, wherein in step 1) the odor profile is selected from a plurality of odors, sourness, smoke, burnt flavors, other flavors; the other flavors include mint flavor, milk flavor, coffee flavor;
and/or the score can be a multi-score system, preferably a 7-score system, and the score is from 1 to 7 according to the intensity of the odor from weak to strong;
and/or, in the step 2), the adsorbent is selected from one or more of Tenax TA, graphitized carbon black, activated carbon and molecular sieve;
and/or the sampling time is 5-60 min, and the sampling flow rate is 50-500 mL/min.
3. The method according to claim 1, wherein in step 3) or 4), the thermal desorption-multidimensional gas chromatography-mass spectrometry sniffing analysis step comprises: carrying out thermal desorption, then separating the sample by a first gas chromatographic column, detecting by a hydrogen flame ion detector and carrying out secondary artificial smell analysis, and determining the cutting time period of the required characteristic taste based on the combination of the primary characteristic taste and the secondary artificial smell in the step 1); and after re-sample introduction and separation through the first gas chromatographic column, selecting a cutting time period, further separating through a second gas chromatographic column, and respectively detecting through a mass spectrum detector and carrying out third artificial smell analysis to determine the characteristic odor components of the environmental smoke.
4. The process according to claim 1, characterized in that in step 3) or 4) the thermal desorption conditions are both: the first-stage thermal desorption temperature is 270-300 ℃;
the desorption time is 6-10 min;
the desorption flow is 15-100 ml/min;
the adsorption temperature of the cold trap is minus 40 to 20 ℃;
the secondary desorption temperature is 270-300 ℃;
the desorption time is 10-15 min;
and/or the first chromatographic column is a non-polar chromatographic column and the second chromatographic column is a polar chromatographic column.
5. The method according to claim 1, wherein in step 3) or 4), the temperature rising program of the first chromatographic column is: keeping the temperature at 40-60 ℃ for 1-5 min, then raising the temperature to 200-230 ℃ at the speed of 2-10 ℃/min, and keeping the temperature for 5-20 min.
6. The method according to claim 1, wherein in step 3) or 4), the temperature rising program of the second chromatographic column is: keeping the temperature at 40-50 ℃ for 1-5 min, then increasing the temperature to the temperature required by the cutting time period at the speed of 4-8 ℃/min, then reducing the temperature to 40-50 ℃ at the cooling speed of 20-120 ℃/min, keeping the temperature for 1-5 min, and increasing the temperature to 230-250 ℃ at the speed of 2-7 ℃/min, and keeping the temperature for 10-30 min.
7. The method of claim 1, wherein in step 3) or step 4), the mass spectrometry conditions are:
transmission line temperature: 230 to 250 ℃;
ionization energy: 65-75eV;
EI source temperature: 220 to 250 ℃;
quadrupole rod temperature: 140-150 ℃;
mass scan range: 33-300 amu.
8. The method according to claim 1, wherein in the step 4), the sampling time is 3 s-30 min, and the sampling flow rate is 50-500 mL/min;
and/or the dilution factor is a ratio between the initial sampling time and the shortened sampling time.
9. The environmental flue gas odor component analysis device is characterized by comprising a sampling pipe (12), a cold trap (11), a first chromatographic column (21), a second chromatographic column (22) and a mass spectrum detector (4) which are sequentially communicated; the sampling pipe (12) and the cold trap (11) are arranged in the thermal desorption instrument (1); the first chromatographic column (21) and the second chromatographic column (22) are arranged in the column incubator (2); a communication pipeline between the first chromatographic column (21) and the second chromatographic column (22) is also provided with CO 2 A cooling valve (23); the device also comprises an olfactory discrimination port (5), wherein the olfactory discrimination port (5) is respectively communicated with the first chromatographic column (21) and the second chromatographic column (22); the device also comprises a hydrogen flame ion detector (3), wherein the hydrogen flame ion detector (3) is connected with the first chromatographic column (21).
10. Use of the ambient smoke odor component analysis apparatus of claim 9 in ambient smoke odor analysis.
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