Method for detecting polycyclic aromatic hydrocarbon in particulate matters in mainstream smoke of cigarette

Abstract

The invention discloses a method for extracting polycyclic aromatic hydrocarbon in particulate matters of main stream smoke of cigarettes and an n-hexane extracting solution of the polycyclic aromatic hydrocarbon in the particulate matters of the main stream smoke of the cigarettes, which is obtained by the extracting method. The extraction method comprises the following steps: heating a glass fiber filter disc capturing the total particulate matters in the main stream smoke of the cigarette at 380-400 DEG C for 6.0-8.0 minutes, and conveying volatilized components into normal hexane at 0 + / -5 DEG C by using carrier gas, so as to obtain a normal hexane extracting solution of polycyclic aromatic hydrocarbon in the particulate matters in the main stream smoke of the cigarette. The extraction method is based on volatile component collection equipment. The volatile component collecting equipment comprises a carrier gas pipeline, a gas flowmeter, a heating device, a material storage cavity, a first gas circuit valve, a collecting device and a cooling device. The invention further discloses a method for detecting the polycyclic aromatic hydrocarbon in the particulate matters in the mainstream smoke of the cigarette.

Description

Technical Field

[0001] The invention belongs to the field of testing technology, and in particular relates to a novel method for collecting and detecting polycyclic aromatic hydrocarbons in particulate matter of mainstream cigarette smoke. Background Art

[0002] PAHs in the particulate matter of mainstream cigarette smoke are the product of incomplete combustion of tobacco under high temperature and hypoxic conditions, and belong to the condensed-ring PAHs in terms of chemical structure. PAHs are genotoxic, mutagenic and carcinogenic, and are identified as the main organic pollutants that affect human health. Currently, about 30 carcinogenic PAHs have been identified in mainstream cigarette smoke, the most typical of which is benzo(a)pyrene, which has the highest carcinogenicity. Therefore, detecting the release of PAHs (especially benzo(a)pyrene) in mainstream cigarette smoke is of great significance to the study of smoking and health.

[0003] The smoke components produced during cigarette combustion are very complex. At present, more than 5,000 smoke components have been detected, among which the content of polycyclic aromatic hydrocarbons such as benzo(a)pyrene is usually at the ng / stick level, and there are a large number of interfering substances. Therefore, how to remove the interference of other coexisting substances, effectively purify the sample and enrich the target analyte has become an important basis and necessary prerequisite for accurately measuring the release of polycyclic aromatic hydrocarbons such as benzo(a)pyrene in mainstream cigarette smoke.

[0004] At present, the more mature method for determining benzo(a)pyrene in cigarette smoke is solid phase extraction-gas chromatography / mass spectrometry, such as the method included in the national standard GB / T 21130-2007 "Determination of benzo(a)pyrene in total particulate matter in cigarette smoke". The standard stipulates that the preparation method of the test solution includes: first, ultrasonically extracting the filter disc that captures the particulate matter of mainstream cigarette smoke with 40mL cyclohexane for 40 minutes; when purifying, transfer 10mL of the extract to the top of the solid phase extraction column and add 30mL cyclohexane twice for elution, and the elution rate is 0.8mL / min~1.0mL / min; when concentrating, all the eluent is rotary evaporated to 0.5mL under the protection of high-purity nitrogen, and then the internal standard is added to obtain the test solution. The above method consumes 70mL of cyclohexane for each sample, and takes more than 80min (extraction, elution and concentration). Therefore, the existing methods have the disadvantages of long sample pretreatment time, cumbersome operation, and consumption of large amounts of organic reagents. Therefore, it is necessary to develop an environmentally friendly, simple to operate, rapid and accurate method for the determination of polycyclic aromatic hydrocarbons such as benzo(a)pyrene in mainstream cigarette smoke. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a novel method for collecting polycyclic aromatic hydrocarbons in the particulate matter of mainstream cigarette smoke, which method requires only a small amount of organic solvent, is short in time, is easy to operate, and the collected polycyclic aromatic hydrocarbons are of high purity and less interference. The present invention also provides a method for detecting polycyclic aromatic hydrocarbons in the particulate matter of mainstream cigarette smoke based on the collection method.

[0006] To this end, the present invention adopts the following technical solution:

[0007] A method for extracting polycyclic aromatic hydrocarbons from particulate matter in mainstream cigarette smoke comprises the following operations:

[0008] The glass fiber filter that captures the total particulate matter in the mainstream cigarette smoke is heated at 380°C to 400°C for 6.0 to 8.0 minutes, and the volatilized components are transported to n-hexane at 0°C±5°C by a carrier gas to obtain the n-hexane extract of polycyclic aromatic hydrocarbons in the particulate matter in the mainstream cigarette smoke.

[0009] Preferably, the extraction method is based on a volatile component collecting device; the volatile component collecting device includes a carrier gas pipeline, a gas flow meter, a heating device, a material storage cavity, a first gas circuit valve, a collecting device, and a cooling device; wherein the gas flow meter is connected and installed on the carrier gas pipeline; a storage cavity for placing the glass fiber filter is provided in the material storage cavity, the storage cavity is connected to the carrier gas pipeline, and the storage cavity is provided with a carrier gas inlet and a carrier gas outlet on two opposite surfaces; the heating device is used to heat the storage cavity; the first gas circuit valve is connected and arranged on the carrier gas pipeline after the material storage cavity; the collecting device includes a collecting bottle containing n-hexane, the collecting bottle is placed in the cooling device and placed at the end of the carrier gas pipeline, and the n-hexane in the collecting bottle covers the end opening of the carrier gas pipeline.

[0010] Preferably, the heating device comprises a heating layer, a temperature sensor and a heater for heating the heating layer, the heating layer is wrapped on the outer wall of the material storage cavity, and the temperature sensor is arranged in the storage cavity; the heater, temperature sensor and controller are all communicatively connected.

[0011] Preferably, the cooling device is selected from a cold trap or an ice bath, more preferably a cold trap.

[0012] Preferably, the cold trap is a condensation trap.

[0013] Preferably, the volatile component collection device further comprises a controller, and the controller is communicatively connected with the gas flow meter, the heating device, and the first gas path valve.

[0014] As a preferred embodiment, the volatile component collection equipment also includes a cleaning device, a second pneumatic valve and a three-way pipe joint, the carrier gas pipeline includes a conveying section, a cleaning section and a collecting section that are connected; the three-way pipe joint includes a first end, a second end and a third end, the first end is connected and installed in the conveying section, the second end is connected and installed in the collecting section, and the third end is connected and installed in the cleaning section; the gas flow meter, the material storage cavity and the first gas circuit valve are connected and arranged on the conveying section; the second gas circuit valve is connected and arranged on the cleaning section, and the collecting bottle is placed at the end of the collecting section; the cleaning device includes an infusion pump and a cleaning bottle with cleaning liquid, the suction port of the infusion pump is placed in the cleaning bottle, and the output port of the infusion pump is connected to the collecting section.

[0015] In the above-mentioned embodiment including the cleaning device, the volatile component collection device also includes a controller, and the controller is communicatively connected with the gas flow meter, the heating device, the first gas circuit valve, and the second gas circuit valve.

[0016] In the above-mentioned embodiment including the cleaning device, the volatile component collection device also includes a controller, and the controller is communicatively connected with the gas flow meter, the heating device, the first gas circuit valve, the second gas circuit valve and the infusion pump.

[0017] When the first gas circuit valve is closed and the second gas circuit valve and the infusion pump are opened, the cleaning of the pipelines in the cleaning section and the collection section can be achieved, avoiding the contamination of the next collection of volatile components by the residual gas in the pipe, thereby improving the collection purity of the volatile component collection equipment.

[0018] Preferably, the glass fiber filter that captures the total particulate matter in the mainstream cigarette smoke is heated at 380° C. for 6.0 min.

[0019] Preferably, the flow rate of the carrier gas is 2-5 mL / min; more preferably 5 mL / min.

[0020] More preferably, the carrier gas is selected from one of compressed air, nitrogen and helium; more preferably nitrogen.

[0021] Preferably, the volume of n-hexane in the collection bottle is 1-2 mL; more preferably 1 mL.

[0022] As a preferred embodiment, the volatilized components are transported into n-hexane at 0°C±2°C by using the carrier gas.

[0023] Preferably, after heating, the first gas circuit valve is closed, the second gas circuit valve and the infusion pump are opened, and the pipeline of the collection section is cleaned with 0.5-1 mL, more preferably 1 mL, of n-hexane, and the n-hexane cleaning liquid is combined with the n-hexane in the collection bottle.

[0024] The total particulate matter in the mainstream cigarette smoke is captured on a glass fiber filter using conventional methods in the art. A feasible implementation scheme is to capture the total particulate matter in the mainstream cigarette smoke on a glass fiber filter using a conventional smoking machine and a smoke collector in accordance with the conditions specified in the national standard GB / T 19609-2024.

[0025] Preferably, the rotary smoking machine captures the total particulate matter of mainstream smoke from 20 cigarettes on a filter with a diameter of 92 mm each time, or the linear smoking machine captures the total particulate matter of mainstream smoke from 5 cigarettes on a filter with a diameter of 44 mm each time.

[0026] When the total particulate matter in the mainstream cigarette smoke is captured on a filter disc with a diameter of 92 mm, the filter disc can be divided into four equal parts, and any one of the four parts can be taken for extraction.

[0027] Optionally, the part of the glass fiber filter that captures the particulate matter can be peeled off and then extracted.

[0028] The method for extracting polycyclic aromatic hydrocarbons from the particulate matter in mainstream cigarette smoke provided by the present invention is based on a novel volatile component collection device. Figure 1 As shown, when the volatile component collection device of the present invention is used, the sample in the storage chamber (for example, a glass fiber filter that captures the total particulate matter in the mainstream smoke of cigarettes) is evenly wrapped in the outer heating layer and heated, and the volatile components are carried to the collection bottle by the carrier gas and absorbed by the absorption solvent (for example, 0℃±5℃, preferably 0℃±2℃ n-hexane) that has been cooled therein, so that the continuous collection of volatile components at a certain temperature can be achieved. In order to reduce the memory effect and the interference with the subsequent sample analysis, the rear end pipeline of the storage chamber (mainly the collection section) can be cleaned by setting the first gas circuit valve and the second gas circuit valve: when the first gas circuit valve is opened and the second gas circuit valve is closed, the volatile components are absorbed; when the first gas circuit valve is closed and the second gas circuit valve is opened, the rear end pipeline of the material storage chamber is cleaned.

[0029] Therefore, the present invention also provides a n-hexane extract of particulate matter in mainstream cigarette smoke prepared by the above extraction method.

[0030] Another object of the present invention is to provide a method for detecting polycyclic aromatic hydrocarbons in the particulate matter of mainstream cigarette smoke, based on gas chromatography-tandem mass spectrometry, using the n-hexane extract of the present invention as the sample to be tested, the standard sample including benzo(a)pyrene, and deuterated benzo(a)pyrene as the internal standard.

[0031] Preferably, the detection method comprises the following steps:

[0032] (1) Capture of total particulate matter in mainstream cigarette smoke

[0033] The total particulate matter in the mainstream cigarette smoke is captured on the glass fiber filter;

[0034] (2) Preparation of test solution

[0035] The glass fiber filter that captures the total particulate matter in the mainstream cigarette smoke is placed in the storage chamber of the volatile component collection device of the present invention, and the n-hexane extract is obtained as the sample to be tested according to the extraction method of the present invention, and deuterated benzo(a)pyrene is added to obtain a test solution;

[0036] (3) Preparation of a series of mixed standard solutions

[0037] Using n-hexane as solvent, a series of mixed standard solutions including PAH standards and internal standards were prepared;

[0038] (4) Determination

[0039] Gas chromatography conditions included:

[0040] Chromatographic column: HP-5MS, 30m×0.25mm×0.25μm;

[0041] Heating program: initial temperature 150 °C, heating to 260 °C at a heating rate of 6 °C / min, holding for 10 min, and then running at 280 °C for 20 min;

[0042] Injection volume: 1 μL;

[0043] Splitless injection;

[0044] Inlet temperature: 280°C;

[0045] Carrier gas: helium;

[0046] Constant flow rate: 1.2mL / min;

[0047] Solvent delay time: 12.0min;

[0048] Mass spectrometry conditions included:

[0049] Ionization method: electron bombardment ion source;

[0050] Ion source temperature: 300°C;

[0051] Transmission line temperature: 300°C;

[0052] Quadrupole temperature: 150°C;

[0053] Monitoring method: Multiple reaction monitoring;

[0054] Under the conditions of gas chromatography and mass spectrometry, the test solution and the series of mixed standard solutions are respectively accurately aspirated and injected into a gas chromatography-tandem mass spectrometer for measurement, and a chromatogram is recorded;

[0055] (5) Data processing and analysis

[0056] The method comprises qualitative and quantitative determination; wherein the qualitative determination comprises determining whether the corresponding polycyclic aromatic hydrocarbons exist in the test solution according to the retention time of the standard, the quantitative and qualitative ion pairs and the corresponding collision energy; the quantitative determination adopts the internal standard method, and the working curve is drawn with the ratio of the peak area of ​​the polycyclic aromatic hydrocarbon standard in the series of mixed standard solutions to the peak area of ​​the internal standard as the ordinate, and the concentration of the polycyclic aromatic hydrocarbon standard in the series of mixed standard solutions as the abscissa; according to the ratio of the peak area of ​​the polycyclic aromatic hydrocarbons in the test solution to the peak area of ​​the internal standard, according to the working curve, the content of the target polycyclic aromatic hydrocarbons in each cigarette is calculated by formula I,

[0057]

[0058] Where, m: the content of target PAHs in each cigarette, ng / cigarette,

[0059] x: The peak area ratio of the target PAHs to the internal standard,

[0060] a: slope of the working curve,

[0061] b: intercept of the working curve,

[0062] V: volume of absorption solvent, mL,

[0063] n: Number of cigarettes smoked, pcs.

[0064] In step (1), the total particulate matter in the mainstream cigarette smoke is captured on the glass fiber filter by conventional methods in the art. A feasible implementation scheme is to capture the total particulate matter in the mainstream cigarette smoke on the glass fiber filter using a conventional smoking machine and a smoke collector according to the conditions specified in the national standard GB / T 19609-2024.

[0065] Preferably, the rotary smoking machine captures the total particulate matter of mainstream smoke from 20 cigarettes on a filter with a diameter of 92 mm each time, or the linear smoking machine captures the total particulate matter of mainstream smoke from 5 cigarettes on a filter with a diameter of 44 mm each time.

[0066] When the total particulate matter in the mainstream smoke of the cigarette is captured on the filter disc with a diameter of 92 mm, the filter disc can be divided into four equal parts, and any one of the parts can be used to perform the operation of step (2).

[0067] Optionally, the part of the glass fiber filter that captures the particulate matter may be peeled off to perform step (2).

[0068] Preferably, the specific operation of step (2) is:

[0069] The glass fiber filter obtained in step (1) and capturing the total particulate matter of mainstream cigarette smoke is placed in the storage chamber of the volatile component collection device, and the temperature of the cooling device is set to 0°C±5°C, preferably 0°C±2°C; 1-2 mL of n-hexane is accurately aspirated and transferred into a collection bottle, and then the collection bottle is placed in the cooling device and placed under the end opening of the carrier gas pipeline collection section, and the end opening is immersed in n-hexane; the first gas circuit valve is closed; the second gas circuit valve is opened, and the gas flow meter is adjusted to set the carrier gas flow rate to 2-5 mL / min; the heating layer is set to 380°C and kept warm for 6.0 min; then the heating is stopped, the first gas circuit valve is closed, the second gas circuit valve is opened, the infusion pump is started, and the carrier gas pipeline collection section is cleaned with 0.5-1 mL of n-hexane, and the cleaning liquid is combined with the n-hexane in the collection bottle to obtain a n-hexane extract; deuterated benzo(a)pyrene is added to obtain a test solution.

[0070] Preferably, the flow rate of the carrier gas is 5 mL / min.

[0071] More preferably, the carrier gas is selected from one of compressed air, nitrogen and helium; more preferably nitrogen.

[0072] Preferably, the volume of n-hexane in the component collection bottle is 1 mL.

[0073] Preferably, the concentration of deuterated benzo(a)pyrene in the test solution is 6.13 ng / mL.

[0074] Preferably, in step (3), the standard is Benz(a)anthracene and benzo(a)pyrene.

[0075] Preferably, in step (3), in the series of mixed standard solutions, The concentration gradient of was 2.17, 4.34, 8.68, 17.36, 43.40, 86.80 and 130.20 ng / mL, the concentration gradient of benzo(a)anthracene was 1.45, 2.90, 5.80, 11.60, 29.00, 58.00 and 87.00 ng / mL, and the concentration gradient of benzo(a)pyrene was 0.94, 1.88, 3.76, 7.52, 18.80, 37.60 and 56.40 ng / mL.

[0076] Also preferably, in the step (3), the concentration of deuterated benzo(a)pyrene in the series of mixed standard solutions is 6.13 ng / mL.

[0077] Preferably, in step (5), The retention time of benzo(a)anthracene was 16.89±0.10min, the quantitative ion pair and collision energy were 228.0>226.0, 38.0ev, and the qualitative ion pair and collision energy were 228.0>224.0, 38.0ev; the retention time of benzo(a)anthracene was 17.04±0.10min, the quantitative ion pair and collision energy were 228.0>226.0, 38.0ev, and the qualitative ion pair and collision energy were 228.0>224.0, 38.0ev; The retention time of deuterated benzo(a)pyrene was 22.89±0.10min, the quantitative ion pair and collision energy were 264.0>260.0, 40.0ev, and the qualitative ion pair and collision energy were 260.0>256.0, 40.0ev.

[0078] In the present disclosure, unless otherwise specified, all solvents (including the solvents of the absorption liquid and the standard solution) are chromatographically pure.

[0079] The present invention uses heating to volatilize polycyclic aromatic hydrocarbons from a glass fiber filter disc, which is absorbed by a small amount of cooled solvent under the carrier gas, and then analyzed by a gas chromatography-tandem mass spectrometer, and the content of polycyclic aromatic hydrocarbons in the particulate matter of mainstream cigarette smoke is qualitatively and quantitatively determined by an internal standard method. After comparative tests, the extraction efficiency of polycyclic aromatic hydrocarbons in the particulate matter of mainstream cigarette smoke provided by the present invention is comparable to that of the traditional method. However, to complete the determination of a sample, the method of the present invention consumes no more than 3mL of n-hexane, and after capturing the total particulate matter of mainstream cigarette smoke, it takes only about 10 minutes to complete the preparation of a test solution. In the existing determination technology, a large amount of solvent extraction is required, and then the extract needs to be purified (such as solid phase extraction) and concentrated, which not only takes a long pre-treatment time, but also has a poor purification effect and is not environmentally friendly. The method of the present invention does not require the glass fiber filter disc with trapped particulate matter to be subjected to solution extraction and subsequent solid phase extraction purification, concentration and other operation steps, and has the advantages of simple and fast operation, green and efficient, and strong matrix removal ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] The present invention will be further described below in conjunction with the accompanying drawings.

[0081] Figure 1 The figure is a schematic diagram of the structure of the volatile component collection device. The reference numerals in the figure are explained as follows:

[0082] 1: carrier gas pipeline; 2: gas flow meter; 3: material storage chamber; 4: storage chamber; 5: first gas circuit valve; 6: collecting bottle; 7: heating layer; 8: cooling device; 9: cleaning device; 10: second pneumatic valve; 13: collecting section; 14: cleaning section.

[0083] Figure 2 The influence of different absorption solvents on the analysis results.

[0084] Figure 3 To investigate the effect of absorption solvent temperature on the analysis results.

[0085] Figure 4 The influence of sample heating time on the analysis results.

[0086] Figure 5 The influence of sample heating temperature on the analysis results.

[0087] Figure 6 The influence of carrier gas type on the analysis results.

[0088] Figure 7 The effect of carrier gas flow rate on the analysis results.

[0089] Figure 8 Typical chromatograms of three PAHs analyzed in cigarette samples using this method.

[0090] Figure 7 and Figure 8 In: Chry: BaA: benzo(a)anthracene; BaP: benzo(a)pyrene.

[0091] Fig. 9 The ultraviolet spectra (200-400 nm) of the n-hexane extracts of the total particulate matter in mainstream smoke of 20 commercially available cigarettes obtained by the method of the present invention and the method of the national standard GB / T 21130-2007 after being diluted 100 times.

[0092] Fig.10 The regression curves are of benzo(a)pyrene content in total particulate matter in mainstream smoke of 20 commercially available cigarettes measured by the method of the present invention and the national standard GB / T 21130-2007 method, respectively, wherein the abscissa is the measured value by the national standard method, and the ordinate is the measured value by the method of the present invention.

[0093] Fig.11 This is a scanning electron microscope photo of the side of the glass fiber filter, where:

[0094] (A) The magnification is 200 times;

[0095] (B) The magnification is 500 times;

[0096] (C) The magnification is 1000 times. DETAILED DESCRIPTION

[0097] The present invention is described below with reference to specific examples. It will be appreciated by those skilled in the art that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention in any way.

[0098] The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials, reagents, etc. used in the following examples are commercially available products unless otherwise specified. The purchase of some reagents and instruments is as follows:

[0099] Gas chromatography-tandem mass spectrometer: Agilent 8890-7000D, equipped with 7693A autosampler;

[0100] Gas chromatography column: HP-5MS, 30m×0.25mm×0.25μm; Agilent.

[0101] In the following examples or research examples, the qualitative and quantitative determination of the PAH extracts were carried out according to the following operating steps:

[0102] Preparation of a series of mixed standard solutions

[0103] Cyclohexane was used as solvent and three kinds of polycyclic aromatic hydrocarbons ( Benzo(a)anthracene and benzo(a)pyrene) standard substances are used as solutes, deuterated benzo(a)pyrene is used as internal standard, and a series of mixed standard solutions containing internal standards of different concentrations are prepared. In the series of mixed standard solutions, The concentration gradient of was 2.17, 4.34, 8.68, 17.36, 43.40, 86.80 and 130.20 ng / mL, the concentration gradient of benzo(a)anthracene was 1.45, 2.90, 5.80, 11.60, 29.00, 58.00 and 87.00 ng / mL, the concentration gradient of benzo(a)pyrene was 0.94, 1.88, 3.76, 7.52, 18.80, 37.60 and 56.40 ng / mL, and the concentration of deuterated benzo(a)pyrene was 6.13 ng / mL.

[0104] Determination

[0105] Gas chromatography conditions included:

[0106] Chromatographic column: HP-5MS, 30m×0.25mm×0.25μm;

[0107] Heating program: initial temperature 150 °C, heating to 260 °C at a heating rate of 6 °C / min, holding for 10 min, and then running at 280 °C for 20 min;

[0108] Injection volume: 1 μL;

[0109] Splitless injection;

[0110] Inlet temperature: 280°C;

[0111] Carrier gas: helium;

[0112] Constant flow rate: 1.2mL / min;

[0113] Solvent delay time: 12.0min;

[0114] Mass spectrometry conditions included:

[0115] Ionization method: electron bombardment ion source;

[0116] Ion source temperature: 300°C;

[0117] Transmission line temperature: 300°C;

[0118] Quadrupole temperature: 150°C;

[0119] Monitoring method: Multiple reaction monitoring;

[0120] Under the conditions of gas chromatography and mass spectrometry, the test solution and the series of standard solutions are respectively accurately aspirated and injected into the gas chromatography-tandem mass spectrometer for measurement, and the chromatogram is recorded;

[0121] Data processing and analysis

[0122] Qualitative determination: Determine whether the corresponding PAHs exist in the test solution based on the retention time of the standard, the quantitative and qualitative ion pairs and the corresponding collision energy; where:

[0123] The retention time was 16.89 ± 0.10 min, the quantitative ion pair and collision energy were 228.0>226.0, 38.0 eV, and the qualitative ion pair and collision energy were 228.0>224.0, 38.0 eV;

[0124] Benz(a)anthracene: retention time is 17.04±0.10min, quantitative ion pair and collision energy are 228.0>226.0, 38.0ev, qualitative ion pair and collision energy are 228.0>224.0, 38.0ev;

[0125] Benzo(a)pyrene: retention time is 23.02±0.10min, quantitative ion pair and collision energy are 252.0>250.0, 40.0ev, qualitative ion pair and collision energy are 250.0>248.0, 40.0ev;

[0126] Deuterated benzo(a)pyrene: retention time is 22.89±0.10min, quantitative ion pair and collision energy are 264.0>260.0, 40.0ev, qualitative ion pair and collision energy are 260.0>256.0, 40.0ev.

[0127] Quantitative determination: The internal standard method was used to draw a working curve with the ratio of the peak area of ​​PAHs in the series of standard solutions to the peak area of ​​the internal standard as the ordinate and the concentration of PAHs in the series of standard solutions as the abscissa; the content of target PAHs in each cigarette was calculated by formula I according to the ratio of the peak area of ​​PAHs in the test solution to the peak area of ​​the internal standard.

[0128]

[0129] Where, m: the content of target PAHs in each cigarette, ng / cigarette,

[0130] x: The peak area ratio of the target PAHs to the internal standard,

[0131] a: slope of the working curve,

[0132] b: intercept of the working curve,

[0133] V: volume of absorption solvent, mL,

[0134] n: Number of cigarettes smoked, unit: cigarettes.

[0135] Example 1: A volatile component collection device

[0136] like Figure 1As shown, a volatile component collection device includes a carrier gas pipeline 1, a gas flow meter 2, a heating device, a material storage cavity 3, a first gas circuit valve 5, a collecting device, a cooling device 8, a cleaning device 9, a second gas circuit valve 10, a three-way pipe joint and a controller. The carrier gas pipeline 1 is used for gas supply, and includes a conveying section, a cleaning section 14 and a collecting section 13 that are connected. The three-way pipe joint includes a first end, a second end and a third end, the first end is connected and installed in the conveying section of the carrier gas pipeline 1, the second end is connected and installed in the collecting section 13, and the third end is connected and installed in the cleaning section 14. The second gas circuit valves 10 are connected and installed on the cleaning section 14. The gas flow meter 2 is connected and installed on the conveying section of the carrier gas pipeline 1. A storage chamber 4 is arranged in the material storage cavity 3, and the storage chamber 4 is used to store solid or liquid samples. The storage chamber 4 is connected to the conveying section of the carrier gas pipeline 1, and a carrier gas inlet and a carrier gas outlet are arranged on two opposite surfaces of the storage chamber 4. The heating device includes a heating layer 7, a temperature sensor and a heater; the heater is used to heat the heating layer 7, the heating layer 7 is wrapped on the outer wall of the material storage cavity 3, and the temperature sensor is arranged in the storage cavity 4. The first gas circuit valve 5 is connected to the conveying section of the carrier gas pipeline 1 after the material storage cavity 3. The collecting device includes a collecting bottle 6 with an absorption liquid placed therein, the collecting bottle 6 is placed at the end of the collecting section 13 of the carrier gas pipeline 1, and the solvent used for absorption in the collecting bottle submerges the end opening of the collecting section 13. The cleaning device 9 includes an infusion pump and a cleaning bottle with a cleaning liquid placed therein. The suction port of the infusion pump is placed in the cleaning bottle, and the output port of the infusion pump is connected to the collecting section 13. The controller is communicatively connected with the gas flowmeter 2, the heater, the temperature sensor, the first gas circuit valve 5 and the second gas circuit valve 10.

[0137] When using the volatile component collection device of this embodiment to collect volatile components, first, move an appropriate amount of absorption liquid (solvent) into the collection bottle 6, place the collection bottle 6 in the cooling device 8 and place it below the end opening of the collection section 13 of the carrier gas pipeline 1, the opening of the collection section 13 is immersed in the absorption liquid, and start the cooling device; then, place the solid or liquid sample in the storage chamber 4 of the material storage chamber 3; open the first gas circuit valve 5, and close the second gas circuit valve 10; finally, the controller turns on the heater, and the heater heats the solid or liquid sample in the storage chamber 4, and the gas in the carrier gas pipeline 1 at a specific flow rate will carry the volatile components in the storage chamber 4 to the collection bottle 6 through the collection section 13, and be absorbed by the absorption liquid. Thus, the volatile components can be collected at a specific temperature.

[0138] After heating, the first gas circuit valve 5 is closed, and the second gas circuit valve 10 and the infusion pump are opened, so that the cleaning section 14 and the collection section 13 can be cleaned, thereby avoiding the residual gas in the pipe from polluting the next collection of volatile components and improving the collection purity of the volatile component collection equipment.

[0139] This research example investigates a method for preparing an extract of polycyclic aromatic hydrocarbons in the particulate matter of mainstream cigarette smoke using the volatile component collection device of Example 1.

[0140] Using the novel volatile component collection device of Example 1, the glass fiber filter that captures the total particulate matter of the mainstream cigarette smoke is placed in the storage chamber 4, and an appropriate amount of absorption solvent is moved into the collection bottle 6, and then the collection bottle 6 is placed in the cooling device 8, and the end opening of the collection section 13 of the carrier gas pipeline 1 is immersed in the absorption solvent in the collection bottle 6; the first valve 5 is opened and the second gas circuit valve 6 is closed, and the controller starts the heater to heat and protect the heating layer 7 for a period of time. During this period, the carrier gas with a specific flow rate in the carrier gas pipeline 1 carries the volatile components volatilized from the glass fiber filter in the storage chamber 4 to the collection bottle 6 through the collection section 13, and is absorbed by the absorption solvent therein. In this way, the continuous collection of polycyclic aromatic hydrocarbon components at the set temperature T (≤T) is achieved. After heating is completed, the first gas circuit valve 5 is closed and the second gas circuit valve 6 is opened, the infusion pump is started, and the cleaning solvent in the cleaning device cleans the collection section 13. The cleaning liquid is combined with the solution in the collection bottle 6 through the collection section to obtain a polycyclic aromatic hydrocarbon extract for gas chromatography-tandem mass spectrometry analysis and determination.

[0141] In the above collection process, factors such as the type and temperature of the absorption solvent, the sample heating temperature and holding time, the type and flow rate of the carrier gas will affect the collection (extraction) efficiency. This study investigated each of the above factors.

[0142] 1. Capture of total particulate matter in mainstream cigarette smoke

[0143] According to the conditions and steps specified in the national standard GB / T 19609-2024, the total particulate matter in the mainstream smoke of 20 cigarettes was captured on a glass fiber filter with a diameter of 92 mm using a turntable smoking machine and a smoke collector.

[0144] 2. Investigation of absorption solvent types

[0145] The extraction solutions were prepared using room temperature acetone, cyclohexane, cyclohexane / acetone mixed solution (1 / 1, v / v) and n-hexane as absorption solvents, heating temperature was 350°C, nitrogen was used as carrier gas, and the flow rate was 2.0 mL / min. Deuterated benzo(a)pyrene was added to each extraction solution as an internal standard to make the concentration of the internal standard 6.13 ng / mL. The qualitative and quantitative determination of polycyclic aromatic hydrocarbons was carried out, and the results are shown in Figure 2 .

[0146] Figure 2It is shown that, except for the slightly lower absorption efficiency of the cyclohexane / acetone mixed solution (1 / 1, v / v), there is no difference in the absorption efficiency of the other several solutions (acetone, cyclohexane and n-hexane). Considering that acetone is a controlled solvent that is easy to make drugs, and cyclohexane has a low freezing point (6.5°C), it is easy to solidify at low temperatures and affect the absorption effect, so n-hexane is preferred as the absorption solvent.

[0147] 3. Investigation of absorption solvent temperature

[0148] With n-hexane as the absorption solvent, the filter heating temperature was 350°C, nitrogen was used as the carrier gas, and the flow rate was 5.0 mL / min. The extraction solutions were prepared at room temperature (25°C) and -2°C respectively. Deuterated benzo(a)pyrene was added to each extract as an internal standard, and the concentration of the internal standard was 6.13 ng / mL. The qualitative and quantitative determination of polycyclic aromatic hydrocarbons was carried out, and the results are shown in Figure 3 .

[0149] Figure 3 It is shown that the absorption efficiency of the absorption solvent at the two temperatures is equivalent, and there is no difference between the two. In order to avoid the influence of room temperature fluctuations or seasonal changes, the temperature of the absorption solvent is subsequently set to -2°C.

[0150] 4. Investigation of filter heating time

[0151] Using -2℃ n-hexane as the absorption solvent, the filter heating temperature was 350℃, nitrogen was used as the carrier gas, and the flow rate was 2.0mL / min. The extraction solutions were prepared under the conditions of heating for 1, 2, 4, 6 and 8min respectively. Deuterated benzo(a)pyrene was added to each extract as an internal standard, and the concentration of the internal standard was 6.13ng / mL. The qualitative and quantitative determination of polycyclic aromatic hydrocarbons was carried out, and the results are shown in Figure 4 .

[0152] Figure 4 It is shown that the detection results of the three target compounds in the first 6 minutes show a continuous upward trend. After heating for 8 minutes, the content of the target compounds has not increased or increased insignificantly. Therefore, the heating time of the filter is preferably 6.0 minutes.

[0153] 5. Investigation of filter heating temperature

[0154] Using -2℃ n-hexane as the absorption solvent, the filter heating time was 6min, nitrogen as the carrier gas, and the flow rate was 2.0mL / min. The extraction solutions were prepared under the conditions of heating temperatures of 230℃, 270℃, 310℃, 350℃ and 380℃ respectively. Deuterated benzo(a)pyrene was added to each extract as an internal standard, and the concentration of the internal standard was 6.13ng / mL. The qualitative and quantitative determination of polycyclic aromatic hydrocarbons was carried out, and the results are shown in Figure 5 .

[0155] Figure 5It is shown that the contents of the three PAHs all reach the highest at 380°C. The boiling points of the three target analytes are between 437-495°C, so lower temperatures are not conducive to the volatilization of the target from the filter. Taking benzo(a)pyrene as an example, when the heating temperature is 380°C, its test results are consistent with the test results obtained by the national standard method. Continuing to increase the temperature will also put forward higher requirements on the sealing performance of the device. Therefore, considering comprehensively, the filter heating temperature is preferably 380°C.

[0156] 6. Investigation of carrier gas type

[0157] The extraction solution was prepared by using -2℃ n-hexane as the absorption solvent, the filter heating temperature was 380℃, the time was 6min, the carrier gas flow rate was 5.0mL / min, and nitrogen and helium were used as carrier gases respectively. Deuterated benzo(a)pyrene was added to each extract as an internal standard, and the concentration of the internal standard was 6.13ng / mL. The qualitative and quantitative determination of polycyclic aromatic hydrocarbons was carried out, and the results are shown in Figure 6 .

[0158] Figure 6 It is shown that there is no difference in the analysis results of the two carrier gases. It is suggested that any inert gas can be used as a carrier gas, including but not limited to nitrogen, helium, compressed air, etc., and nitrogen, which has a high safety factor, is cheap, and is commonly used in laboratories, is preferably used as a carrier gas.

[0159] 7. Investigation of carrier gas flow rate

[0160] The extraction solutions were prepared using -2℃ n-hexane as the absorption solvent, the filter heating temperature was 380℃, the time was 6min, and nitrogen was used as the carrier gas at nitrogen flow rates of 0, 1, 2, 5, 10 and 15mL / min. Deuterated benzo(a)pyrene was added to each extract as an internal standard to a concentration of 6.13ng / mL. The qualitative and quantitative determination of polycyclic aromatic hydrocarbons was performed, and the results are shown in Figure 7 .

[0161] Figure 7 It is shown that when there is no carrier gas (carrier gas flow rate is 0 mL / min), the device can still achieve the purpose of collecting volatile target substances. As the carrier gas flow rate increases, the absorption effect of the target substance increases first and then decreases, and reaches the maximum at 2-5 mL / min. Therefore, the carrier gas flow rate is preferably 2-5 mL / min, and more preferably 5 mL / min.

[0162] In summary, the optimized conditions for preparing the extract are: the absorption solvent is n-hexane at -2°C, the sample heating temperature and time are 380°C and 6.0 min, the carrier gas type and flow rate are nitrogen and 2-5 mL / min, more preferably 5 mL / min.

[0163] Under the above conditions, a cigarette sample was measured and the chromatograms obtained with retention times of 16.6-17.4min and 22.6-23.6min were as follows Figure 8 shown. Figure 8 It is shown that the three PAHs are baseline separated without matrix interference, which indicates that the extraction method based on the novel volatile component collection device of the present invention has good extraction specificity for PAHs and can well purify the interferences in the total particulate matter of captured cigarette smoke.

[0164] Study Example 2: Methodological Review

[0165] Based on Study Example 1, the present invention establishes a method for detecting polycyclic aromatic hydrocarbons in particulate matter in mainstream cigarette smoke, comprising the following steps:

[0166] (1) Capture of total particulate matter in mainstream cigarette smoke

[0167] According to the conditions specified in the national standard GB / T 19609-2024, the total particulate matter of the mainstream smoke of 20 cigarettes is captured on a filter with a diameter of 92 mm using a rotary smoking machine and a smoke collector, or the total particulate matter of the mainstream smoke of 5 cigarettes is captured on a filter with a diameter of 44 mm using a linear smoking machine and a smoke collector.

[0168] (2) Preparation of test solution

[0169] The glass fiber filter obtained in step (1) and containing the total particulate matter of the mainstream cigarette smoke is placed in the storage chamber 4 of the volatile component collection device of Example 1, and the temperature of the cooling device is set to -2°C; 1 mL of n-hexane is accurately aspirated and transferred into the collecting bottle 6, and then the collecting bottle 6 is placed in the cooling device and placed under the end opening of the collecting section 13, so that the end opening is immersed in the n-hexane; the second gas circuit valve 10 is closed; the first gas circuit valve 5 is opened, and the gas flowmeter 2 is adjusted to set the nitrogen flow rate to 5 mL / min; the heating temperature is set to 380°C and kept warm for 6.0 min; then the heating of the heating layer is stopped, the first gas circuit valve 5 is closed, the second gas circuit valve 10 is opened, and the collecting section 13 is cleaned with 0.5 mL of n-hexane, and the cleaning liquid is combined with the n-hexane in the collecting bottle 6 to obtain a n-hexane extract; deuterated benzo(a)pyrene is added as an internal standard so that the concentration of the internal standard is 6.13 ng / mL to obtain a test solution.

[0170] (3) Preparation of a series of mixed standard solutions

[0171] Cyclohexane was used as solvent and three kinds of polycyclic aromatic hydrocarbons ( Benzo(a)anthracene and benzo(a)pyrene) standard substances are used as solutes, deuterated benzo(a)pyrene is used as internal standard, and a series of mixed standard solutions containing internal standards of different concentrations are prepared. In the series of mixed standard solutions, The concentration gradient of was 2.17, 4.34, 8.68, 17.36, 43.40, 86.80 and 130.20 ng / mL, the concentration gradient of benzo(a)anthracene was 1.45, 2.90, 5.80, 11.60, 29.00, 58.00 and 87.00 ng / mL, the concentration gradient of benzo(a)pyrene was 0.94, 1.88, 3.76, 7.52, 18.80, 37.60 and 56.40 ng / mL, and the concentration of deuterated benzo(a)pyrene was 6.13 ng / mL.

[0172] (4) Determination

[0173] Gas chromatography conditions included:

[0174] Chromatographic column: HP-5MS, 30m×0.25mm×0.25μm;

[0175] Heating program: initial temperature 150 °C, heating to 260 °C at a heating rate of 6 °C / min, holding for 10 min, and then running at 280 °C for 20 min;

[0176] Injection volume: 1 μL;

[0177] Splitless injection;

[0178] Inlet temperature: 280°C;

[0179] Carrier gas: helium;

[0180] Constant flow rate: 1.2mL / min;

[0181] Solvent delay time: 12.0min;

[0182] Mass spectrometry conditions included:

[0183] Ionization method: electron bombardment ion source;

[0184] Ion source temperature: 300°C;

[0185] Transmission line temperature: 300°C;

[0186] Quadrupole temperature: 150°C;

[0187] Monitoring method: Multiple reaction monitoring;

[0188] Under the conditions of gas chromatography and mass spectrometry, the test solution and the series of standard solutions are respectively accurately aspirated and injected into a gas chromatography-tandem mass spectrometer for measurement, and a chromatogram is recorded;

[0189] (5) Data processing and analysis

[0190] Includes qualitative and quantitative determination;

[0191] Wherein, the qualitative determination includes determining whether the corresponding polycyclic aromatic hydrocarbons exist in the test solution according to the retention time of the standard and the quantitative and qualitative ion pairs and the corresponding collision energy. Wherein:

[0192] The retention time was 16.89 ± 0.10 min, the quantitative ion pair and collision energy were 228.0>226.0, 38.0 eV, and the qualitative ion pair and collision energy were 228.0>224.0, 38.0 eV;

[0193] Benz(a)anthracene: retention time is 17.04±0.10min, quantitative ion pair and collision energy are 228.0>226.0, 38.0ev, qualitative ion pair and collision energy are 228.0>224.0, 38.0ev;

[0194] Benzo(a)pyrene: retention time is 23.02±0.10min, quantitative ion pair and collision energy are 252.0>250.0, 40.0ev, qualitative ion pair and collision energy are 250.0>248.0, 40.0ev;

[0195] Deuterated benzo(a)pyrene: retention time is 22.89±0.10min, quantitative ion pair and collision energy are 264.0>260.0, 40.0ev, qualitative ion pair and collision energy are 260.0>256.0, 40.0ev.

[0196] The quantitative determination adopts the internal standard method, with the ratio of the peak area of ​​PAHs in the series of standard solutions to the peak area of ​​the internal standard as the ordinate, and the concentration of PAHs in the series of mixed standard solutions as the abscissa, to draw a working curve; according to the ratio of the peak area of ​​the target PAHs in the test solution to the peak area of ​​the internal standard, the content of the target PAHs in each cigarette is calculated by formula I,

[0197]

[0198] Where, m: the content of target PAHs in each cigarette, ng / cigarette,

[0199] x: The peak area ratio of the target PAHs to the internal standard,

[0200] a: slope of the working curve,

[0201] b: intercept of the working curve,

[0202] V: volume of absorption solvent, mL,

[0203] n: Number of cigarettes smoked, pcs.

[0204] 1. Linear range, detection limit and quantification limit

[0205] According to the above (3) preparation of the series of mixed standard solutions, (4) determination and (5) data processing, the series of mixed standard solutions were determined, and the working curve (weighted as 1 / x) was made by comparing the peak area ratio of the three PAH standards and the internal standard to the concentration of the PAH standards. The detection limit and quantification limit were calculated at 3 times and 10 times the signal-to-noise ratio, respectively. The results are shown in Table 1.

[0206] As shown in Table 1, the three target analytes had a good linear relationship within their respective linear ranges, the square of the linear correlation coefficient of the working curve was not less than 0.9963, and the detection limit (LOD) and quantification limit (LOQ) of the target analytes were between 0.19 and 0.69 ng / mL and 0.65 and 2.31 ng / mL, respectively.

[0207] Table 1 Linear range, working curve, detection limit and quantification limit of the detection method of the present invention

[0208]

[0209] 2. Repeatability and precision

[0210] Take 3 samples of the same brand of cigarettes and test them according to the established detection method for PAHs in the particulate matter of mainstream cigarette smoke within 1 day. Calculate the content of PAHs in each cigarette by the standard working curve and formula I, and calculate the intra-day relative standard deviation. For 3 consecutive days, measure the same brand of cigarette samples every day according to the method of the present invention, and calculate the inter-day relative standard deviation. The results are shown in Table 2.

[0211] The data in Table 2 show that the intra-day and inter-day precisions of the target analyte are no more than 5.1% and 6.0%, respectively, indicating that the detection method of the present invention can meet the daily detection requirements of PAHs in the particulate matter of mainstream cigarette smoke in terms of repeatability and stability.

[0212] Table 2 Precision data of the detection method of the present invention (%)

[0213]

[0214] 3. Impurity removal effect

[0215] In order to further verify the impurity removal effect of this method, 20 commercially available samples were pre-treated using this method and the national standard GB / T21130-2007 method, and the obtained sample solutions (n-hexane extracts) were diluted 100 times and then subjected to UV spectral analysis. The results are shown in Fig. 9 shown.

[0216] The wavelength range of 200 to 400 nm is mostly the absorption peaks of tar, alkaloids and other ultraviolet absorbing compounds (collectively referred to as interfering matrices). Fig. 9 It is shown that the absorption intensity of most of the n-hexane extracts obtained by the method in the wavelength range of 200-400 nm is significantly weaker than that of the extracts obtained by the national standard method, for example Fig. 9 (2), (3), (7), (8), (9), (11), (12), (13), (18), (19) and (20) in the above table. This indicates that the interfering matrix content in the n-hexane extract obtained by the present method is lower, that is, the method of the present invention has a better ability to remove interfering substances. In addition, compared with the extract obtained by the national standard method, the n-hexane extract obtained by the present method does not show the phenomenon of enhanced ultraviolet absorption. Therefore, the overall impurity removal ability of the present method is better than that of the national standard method.

[0217] 4. Accuracy test

[0218] In order to compare the accuracy of the results of the method of the present invention with the national standard method, the results of the mainstream smoke of the above 20 commercially available cigarettes were compared by using benzo(a)pyrene as a representative. The results are shown in Table 1. Fig.10 .

[0219] Depend on Fig.10 As shown, the linear relationship between the results of the method of the present invention and the national standard method for determining benzo(a)pyrene is good, the linear equation is y=0.9909x+0.1846, the square of the linear correlation coefficient is 0.9732, and the standard deviation of the determination results is less than 10%. It shows that the method of the present invention has good consistency with the national standard method, and the method of the present invention is accurate and reliable. Compared with the national standard method, the method of the present invention is simpler to operate, the time is greatly shortened, and the solvent consumption is less. It is a simple, fast, green and efficient detection method.

[0220] Example 2

[0221] The same cigarette sample was smoked using a rotary smoking machine and a linear smoking machine, respectively. According to step (1) of the method described in Research Example 2, the total particulate matter in the mainstream smoke was captured on glass fiber filters with diameters of 92 mm and 44 mm, respectively. The 92 mm filter was then divided into four equal parts and one of them was taken to perform the subsequent steps (2) to (5) according to the method described in Research Example 2, and the 44 mm filter was directly used to perform the subsequent steps (2) to (5) according to the method described in Research Example 2. The results are shown in Table 3.

[0222] The data in Table 3 show that the relative deviation of the results obtained by analyzing the same sample with two types of smoking machines is between 0.40% and 1.59%, indicating that there is no difference in the test results of the same sample with different types of smoking machines.

[0223] Table 3 Test results of the same sample analyzed by two types of smoking machines (ng / cigarette)

[0224]

[0225] Embodiment 3:

[0226] The side morphology of the glass fiber filter was observed using a scanning electron microscope. Fig.11 shown. Fig.11 It is shown that the filter disc is made of glass fiber stacked layer by layer, each layer is made of glass fiber with a larger diameter as the skeleton and filled with glass fiber with a thinner diameter, and the thickness of each layer is about 40-60 microns. It can also be found that there are obvious stratification and dividing lines between the layers of the filter disc. Therefore, the fiber layer with trapped particulate matter is creatively peeled off, and then the steps (2) to (5) of the method described in Research Example 2 are followed. The results of the three polycyclic aromatic hydrocarbons obtained are shown in Table 4.

[0227] Table 4 Test results obtained by different filter processing methods (ng / piece)

[0228]

[0229] The data in Table 4 show that for the same sample, the relative deviation of the results obtained with and without the filter stripping is less than 10%, indicating that there is no difference in the test results of the same sample after the filter stripping. The filter stripping can reduce the volume, making it easier to put the filter into the storage chamber of the volatile component collection device.

Claims

1. A method for extracting polycyclic aromatic hydrocarbons from particulate matter in mainstream cigarette smoke, comprising the following operations: The glass fiber filter that captures the total particulate matter in the mainstream cigarette smoke is heated at 380°C to 400°C for 6.0 to 8.0 minutes, and the volatilized components are transported to n-hexane at 0°C±5°C by a carrier gas to obtain the n-hexane extract of polycyclic aromatic hydrocarbons in the particulate matter in the mainstream cigarette smoke.

2. The extraction method according to claim 1, characterized in that The extraction method is based on a volatile component collection device; the volatile component collection device includes a carrier gas pipeline, a gas flow meter, a heating device, a material storage cavity, a first gas circuit valve, a collection device, and a cooling device; wherein the gas flow meter is connected and installed on the carrier gas pipeline; a storage cavity for placing the glass fiber filter is provided in the material storage cavity, the storage cavity is connected to the carrier gas pipeline, and the storage cavity is provided with a carrier gas inlet and a carrier gas outlet on two opposite surfaces; the heating device is used to heat the storage cavity; the first gas circuit valve is connected and arranged on the carrier gas pipeline after the material storage cavity; the collection device includes a collection bottle with n-hexane placed, the collection bottle is placed in the cooling device and placed at the end of the carrier gas pipeline, and the n-hexane in the collection bottle covers the end opening of the carrier gas pipeline; Preferably, the heating device comprises a heating layer, a temperature sensor and a heater for heating the heating layer, the heating layer is wrapped on the outer wall of the material storage cavity, and the temperature sensor is arranged in the storage cavity; the heater, the temperature sensor and the controller are all communicatively connected; Preferably, the cooling device is selected from a cold trap or an ice bath, more preferably a cold trap; Also preferably, the cold trap is a condensation trap; Preferably, the volatile component collection device further comprises a controller, and the controller is communicatively connected with the gas flow meter, the heating device, and the first gas path valve.

3. The extraction method according to claim 2, characterized in that The volatile component collection device also includes a cleaning device, a second pneumatic valve and a three-way pipe joint, the carrier gas pipeline includes a conveying section, a cleaning section and a collecting section that are connected; the three-way pipe joint includes a first end, a second end and a third end, the first end is connected and installed in the conveying section, the second end is connected and installed in the collecting section, and the third end is connected and installed in the cleaning section; the gas flow meter, the material storage cavity and the first gas circuit valve are connected and arranged on the conveying section; the second gas circuit valve is connected and arranged on the cleaning section, and the collecting bottle is placed at the end of the collecting section; the cleaning device includes an infusion pump and a cleaning bottle with a cleaning liquid placed therein, the suction port of the infusion pump is placed in the cleaning bottle, and the output port of the infusion pump is connected to the collecting section; Preferably, the volatile component collection device further comprises a controller, and the controller is communicatively connected with the gas flow meter, the heating device, the first gas path valve, and the second gas path valve; Also preferably, the volatile component collection device further comprises a controller, and the controller is communicatively connected with the gas flow meter, the heating device, the first gas circuit valve, the second gas circuit valve and the infusion pump.

4. The extraction method according to claim 1, characterized in that The glass fiber filter that captured the total particulate matter in the mainstream cigarette smoke was heated at 380°C for 6.0 min; Preferably, the flow rate of the carrier gas is 2 to 5 mL / min; more preferably 5 mL / min; More preferably, the carrier gas is selected from one of compressed air, nitrogen and helium; more preferably nitrogen; Preferably, the volume of n-hexane is 1 to 2 mL; more preferably 1 mL; Preferably, the volatilized components are transported into n-hexane at 0°C±2°C, more preferably -2°C, by the carrier gas.

5. The extraction method according to claim 3, characterized in that After heating, close the first gas circuit valve, open the second gas circuit valve, start the infusion pump, and clean the pipeline of the collection section with 0.5-1 mL, more preferably 1 mL, of n-hexane, and combine the n-hexane cleaning liquid with the n-hexane in the collection bottle.

6. The extraction method according to claim 1, characterized in that The total particulate matter in the mainstream cigarette smoke is captured in a glass fiber filter by a conventional method in the art; Optionally, according to the conditions specified in the national standard GB / T 19609-2024, the total particulate matter of the mainstream smoke of the cigarette is captured on a glass fiber filter using a conventional smoking machine and a smoke collector; preferably, the rotary smoking machine captures the total particulate matter of the mainstream smoke of 20 cigarettes on a filter with a diameter of 92 mm each time, or the linear smoking machine captures the total particulate matter of the mainstream smoke of 5 cigarettes on a filter with a diameter of 44 mm each time; Optionally, when the total particulate matter in the mainstream cigarette smoke is captured on a filter disc with a diameter of 92 mm, the filter disc can be divided into four equal parts, and any one of the four parts can be taken for extraction; Optionally, the part of the glass fiber filter that captures the particulate matter can be peeled off and then extracted.

7. A n-hexane extract of particulate matter in mainstream cigarette smoke, prepared by the extraction method according to any one of claims 1 to 6.

8. A method for detecting polycyclic aromatic hydrocarbons in particulate matter in mainstream cigarette smoke, based on gas chromatography-tandem mass spectrometry, using the n-hexane extract of claim 7 as the sample to be tested, the standard substance comprising benzo(a)pyrene, and deuterated benzo(a)pyrene as the internal standard.

9. The detection method according to claim 8, characterized in that: The detection method comprises the following steps: (1) Capture of total particulate matter in mainstream cigarette smoke The total particulate matter in the mainstream cigarette smoke is captured on the glass fiber filter; (2) Preparation of test solution The glass fiber filter that captures the total particulate matter in the mainstream cigarette smoke is placed in the storage chamber of the volatile component collection device according to claim 2 or 3, and the n-hexane extract is obtained as a sample to be tested according to the extraction method described in any one of claims 1 to 6, and deuterated benzo(a)pyrene is added to obtain a test solution; (3) Preparation of a series of mixed standard solutions Using n-hexane as solvent, a series of mixed standard solutions including PAH standards and internal standards were prepared; (4) Determination Gas chromatography conditions included: Chromatographic column: HP-5MS, 30m×0.25mm×0.25μm; Heating program: initial temperature 150 °C, heating to 260 °C at a heating rate of 6 °C / min, holding for 10 min, and then running at 280 °C for 20 min; Injection volume: 1 μL; Splitless injection; Inlet temperature: 280°C; Carrier gas: helium; Constant flow rate: 1.2mL / min; Solvent delay time: 12.0min; Mass spectrometry conditions included: Ionization method: electron bombardment ion source; Ion source temperature: 300°C; Transmission line temperature: 300°C; Quadrupole temperature: 150°C; Monitoring method: Multiple reaction monitoring; Under the conditions of gas chromatography and mass spectrometry, the test solution and the series of mixed standard solutions are respectively accurately aspirated and injected into a gas chromatography-tandem mass spectrometer for measurement, and a chromatogram is recorded; (5) Data processing and analysis The method comprises qualitative and quantitative determination; wherein the qualitative determination comprises determining whether the corresponding polycyclic aromatic hydrocarbons exist in the test solution according to the retention time of the standard, the quantitative and qualitative ion pairs and the corresponding collision energy; the quantitative determination adopts the internal standard method, and the working curve is drawn with the ratio of the peak area of ​​the polycyclic aromatic hydrocarbon standard in the series of mixed standard solutions to the peak area of ​​the internal standard as the ordinate, and the concentration of the polycyclic aromatic hydrocarbon standard in the series of mixed standard solutions as the abscissa; according to the ratio of the peak area of ​​the polycyclic aromatic hydrocarbons in the test solution to the peak area of ​​the internal standard, according to the working curve, the content of the target polycyclic aromatic hydrocarbons in each cigarette is calculated by formula I, Where, m: the content of target PAHs in each cigarette, ng / cigarette, x: The peak area ratio of the target PAHs to the internal standard, a: slope of the working curve, b: intercept of the working curve, V: volume of absorption solvent, mL, n: Number of cigarettes smoked, pcs.

10. The detection method according to claim 9, characterized in that: The step (1) is to capture the total particulate matter of the mainstream smoke of the cigarette on a glass fiber filter disc by a conventional method in the art; optionally, according to the conditions specified in the national standard GB / T 19609-2024, a conventional smoking machine and a smoke collector are used to capture the total particulate matter of the mainstream smoke of the cigarette on the glass fiber filter disc; preferably, the rotary smoking machine captures the total particulate matter of the mainstream smoke of 20 cigarettes on a filter disc with a diameter of 92 mm each time, or the linear smoking machine captures the total particulate matter of the mainstream smoke of 5 cigarettes on a filter disc with a diameter of 44 mm each time; Optionally, when the total particulate matter in the mainstream cigarette smoke is captured on a filter disc with a diameter of 92 mm, the filter disc can be divided into four equal parts, and any one of the four parts can be used to perform the operation of step (2); Optionally, the part of the glass fiber filter that captures the particulate matter may be peeled off to perform step (2).

11. The detection method according to claim 9, characterized in that: The specific operation of step (2) is: The glass fiber filter obtained in step (1) and capturing the total particulate matter of the mainstream cigarette smoke is placed in the storage chamber of the volatile component collection device, and the temperature of the cooling device is set to 0°C ± 5°C, preferably 0°C ± 2°C, and more preferably -2°C; 1-2 mL of n-hexane is accurately drawn and transferred into a collection bottle, and then the collection bottle is placed in the cooling device and placed under the end opening of the carrier gas pipeline collection section, and the end opening is immersed in n-hexane; the first gas circuit valve is closed; the second gas circuit valve is opened, and the gas flow meter is adjusted to set the carrier gas flow rate to 2-5 mL / min; the heating layer is set to 380°C and kept warm for 6.0 min; then the heating is stopped, the first gas circuit valve is closed, the second gas circuit valve is opened, the infusion pump is started, and the carrier gas pipeline collection section is cleaned with 0.5-1 mL of n-hexane, and the cleaning liquid is combined with the n-hexane in the collection bottle to obtain a n-hexane extract; deuterated benzo(a)pyrene is added to obtain a test solution; Preferably, the flow rate of the carrier gas is 5 mL / min; More preferably, the carrier gas is selected from one of compressed air, nitrogen and helium; more preferably nitrogen; Preferably, the volume of n-hexane in the component collection bottle is 1 mL; Preferably, the concentration of deuterated benzo(a)pyrene in the test solution is 6.13 ng / mL.

12. The detection method according to claim 9, characterized in that: In the step (3), the standard is Benz(a)anthracene and benzo(a)pyrene; Preferably, in step (3), in the series of mixed standard solutions, The concentration gradient of was 2.17, 4.34, 8.68, 17.36, 43.40, 86.80 and 130.20 ng / mL, the concentration gradient of benzo(a)anthracene was 1.45, 2.90, 5.80, 11.60, 29.00, 58.00 and 87.00 ng / mL, and the concentration gradient of benzo(a)pyrene was 0.94, 1.88, 3.76, 7.52, 18.80, 37.60 and 56.40 ng / mL; Also preferably, in the step (3), the concentration of deuterated benzo(a)pyrene in the series of mixed standard solutions is 6.13 ng / mL.

13. The detection method according to claim 9, characterized in that: In the step (5), The retention time of benzo(a)anthracene was 16.89±0.10min, the quantitative ion pair and collision energy were 228.0>226.0, 38.0ev, and the qualitative ion pair and collision energy were 228.0>224.0, 38.0ev; the retention time of benzo(a)anthracene was 17.04±0.10min, the quantitative ion pair and collision energy were 228.0>226.0, 38.0ev, and the qualitative ion pair and collision energy were 228.0>224.0, 38.0ev; The retention time of deuterated benzo(a)pyrene was 22.89±0.10min, the quantitative ion pair and collision energy were 264.0>260.0, 40.0ev, and the qualitative ion pair and collision energy were 260.0>256.0, 40.0ev.

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