CN104133031A - Method and device for determination of cigarette smoke benzo[alpha]pyrene by on-line solid phase extraction - Google Patents
Method and device for determination of cigarette smoke benzo[alpha]pyrene by on-line solid phase extraction Download PDFInfo
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Abstract
Belonging to the technical field of analytical chemistry, the invention discloses a method and device for detection of cigarette smoke benzo[alpha]pyrene. Including sample preparation and analysis, the detection method of benzo[alpha]pyrene specifically comprises: conducting trapping by a filter disc, adding an organic solvent to conduct ultrasonic shaking so as to obtain an analysis sample; separating the sample by a liquid chromatogram, cutting the needed outflow component into a gas chromatogram, and performing adsorption by a solid phase extraction column; and then starting GC-MS, and bringing the to-be-tested component into a capillary separation column to perform analysis. The device is a gas chromatograph-mass spectrometer with an on-line solid phase extraction purification function, wherein the solvent treatment between the liquid chromatogram and the gas chromatogram is solid phase extraction. With the device provided by the invention, efficient purification of the sample and larger volume sample injection of the gas chromatogram can be realized. For ultra low content samples, components subjected to liquid phase separation can be accumulated repeatedly to an ideal analysis amount and then transferred to the gas chromatogram for analysis. While achieving efficient purification of the sample, the analysis sensitivity is greatly improved.
Description
Technical field
The invention belongs to technical field of analytical chemistry, be specifically related to a kind of cigarette smoke benzo [α] pyrene detection method and device thereof.
Background technology
Smoking is harmful to your health has at present been undisputable fact, and research both at home and abroad shows: the chemical substance that smoking mainly discharges from result of combustion of tobacco healthy impact.The objectionable constituent of cigarette smoke grain in mutually mainly contain condensed-nuclei aromatics class, unit phenol and polyatomic phenol (as catechol), phase Free Radicals, polonium 210, uranium, nickel, the cadmiums etc. such as tobacco-specific nitrosamine, heterogeneous cyclic amine, naphthylamines, other nitrosamines, benzo [α] pyrene.In numerous harmful ingredients in flue gas, benzo [α] pyrene has the highest carcinogenic activity.
The content of cigarette smoke benzo [α] pyrene is very low, and flue gas sample matrices is very complicated, and the sample substrate of high complexity tends to various analytic signals to produce serious interference, and conventional instrument method is difficult to meet the requirement of Accurate Determining.Realize the Accurate Determining of trace benzo [α] pyrene in cigarette smoke, need adopt high-sensitive modern instrument method and need to sample, purify in advance.The method of measuring at present cigarette smoke benzo [α] pyrene mainly contains High Performance Liquid Chromatography with Fluorescence Detection (HPLC-FLD) and gas chromatography-mass spectrum (GC-MS) method.Because GC-MS method has higher selectivity than HPLC method, at present tobacco business standard GB T21130-2007 adopt " silicagel column Solid phase extraction-Gc-ms " to measure benzo [α] pyrene in cigarette smoke.The off-line Solid phase extraction troublesome poeration adopting, introduces error component many, and solvent consumption is large; Therefore setting up a kind of flue gas benzo [α] pyrene assay method more convenient, environmental protection is necessary.
Summary of the invention
The invention provides a kind of on-line solid phase extraction and purify, gas chromatography-mass spectrum (GC-MS) is measured the method for cigarette smoke benzo [α] pyrene content.The method sample purification effect and sensitivity are all improved a lot than classic method, and the mensuration that can be benzo in cigarette smoke [α] pyrene content provides method accurately and reliably, meanwhile, provide a kind of new equipment that completes described benzo [α] pyrene detection method
The technical solution used in the present invention is as follows:
A kind of gas chromatography-mass spectrography device with on-line solid phase extraction purification function, comprise liquid chromatographic system, gas chromatography-mass spectrum system, numerical control T-valve and solid-phase extraction column, described liquid chromatographic system comprises the pump connecting successively, injector, chromatographic column and detecting device, between described liquid chromatographic system and gas chromatography-mass spectrum system, being provided with can be for the numerical control T-valve of component cutting, the solid-phase extraction column of being made by exotic material is housed in the injection port of gas chromatography-mass spectrum system, solid-phase extraction column by post web member respectively with solvent exhaust valve, separating column is connected.
Exotic material described in technical solution of the present invention is a kind of in anti-phase exotic material, multi-walled carbon nano-tubes, NACF, polyacrylate clad material and functional mesoporous material.
The present invention also provides a kind of method of measuring cigarette smoke benzo [α] pyrene with on-line solid phase extraction, uses said apparatus, comprises sample collection and preparation, analysis, step specific as follows:
A, sample collection and preparation: with filter disc, trap benzo [α] pyrene, the filter disc after trapping is added containing in the organic solvent of interior mark (deuterium band benzo [α] pyrene), ultrasonic concussion 30～50min obtains sample;
B, analysis: the sample that steps A is made enters into liquid chromatographic separation system, separated through liquid-phase chromatographic column post by pump transport flow, the outflow component that contains benzo [α] pyrene is cut in gas chromatography by numerical control T-valve, and remainder enters waste collecting device; The part of incision gas chromatography, by the solid-phase extraction column in injection port, allows benzo [α] pyrene be adsorbed on solid-phase extraction column, and mobile phase flows out from solvent exhaust valve; The complete rear startup GC-MS of enrichment, heats up and allows the gasification of benzo [α] pyrene and bring capillary separation column separation into by carrier gas, and Mass Spectrometer Method is quantitative.
Filter disc in technical solution of the present invention described in steps A is 92mm cambridge filter or 44mm cambridge filter.
Organic solvent in technical solution of the present invention described in steps A is a kind of in cyclohexane, methylene chloride and acetone.
The mobile phase A in mutually by pump transport flow in technical solution of the present invention described in step B is a kind of in acetonitrile-water, acetonitrile, first alcohol and water, wherein not restriction of concrete ratio in acetonitrile-water.
In technical solution of the present invention, by pump transport flow, the Mobile phase B in is mutually a kind of in water, methyl alcohol and ethanol to step B.
In technical solution of the present invention, further preferably with on-line solid phase extraction, measure the method for cigarette smoke benzo [α] pyrene, comprise the steps:
(1) flue gas trapping: flue gas trapping is pressed the condition of GB/T 19609-2004, Cigarette is in relative humidity 60 ± 5%, balance 48h under the condition that temperature is 22 ± 2 ℃; Every mouthful of suction is spaced apart 60s, and suction time is 2s, and suction capacity is 35 ± 0.3mL, aspirates 20 cigarette, with 92mm cambridge filter trapping flue gas TPM;
(2) sample extraction: have the cambridge filter of mainstream smoke total particulate matter to put into the band plug conical flask of 150mL trapping, accurately add tri-grades of inner mark solutions of people 1mL with transfer pipet, accurately add 40mL cyclohexane, ultrasonic concussion 40min; Wherein, in described, be designated as deuterated benzo [α] pyrene;
(3) liquid chromatography is separated: chromatographic column is C18 reverse-phase chromatographic column, 2.1 * 250mm, 3.5 μ m; 40 ℃ of column temperatures; Mobile phase is acetonitrile/water, 70/30%; Flow velocity 0.6mL/min; Sampling volume is 20 μ L; Sample enters into liquid chromatographic system, separated through liquid-phase chromatographic column separating column by pump transport flow, and the outflow component that contains benzo [α] pyrene is cut in gas chromatography by numerical control T-valve, and remainder enters waste liquid;
(4) part that is cut into gas chromatography enters the injection port of gas chromatography, by the solid-phase extraction column in injection port, allow benzo [α] pyrene be adsorbed on solid-phase extraction column, mobile phase flows out from solvent exhaust valve, then with carrier gas, dry up the water on solid-phase extraction column, and close solvent exhaust valve;
(5) gas chromatography-mass spectrometry analysis: the complete rear startup GC-MS of enrichment, heat up and allow the gasification of benzo [α] pyrene and bring capillary separation column separation into by carrier gas, Mass Spectrometer Method is quantitative; Wherein, gas chromatography chromatographic column is HP-5MS capillary chromatographic column, 0.25mm * 30m, 0.25 μ m; 280 ℃ of injector temperatures, Splitless injecting samples, carrier gas is helium, constant current flow 1.2mL/min; Chromatographic column heating schedule: 150 ℃ of initial temperatures, with 6 ℃/min, rise to 280 ℃, keep 20min; Mass detector condition is: electron bombardment ionization source; 230 ℃ of ion source temperatures, 280 ℃ of transmission line temperature, quality of scanning scope 50～400amu, sweep spacing 0.5s.Under this chromatographic condition, the chromatogram of actual sample is shown in Fig. 2.
Sample enters liquid chromatographic system by injector, enters liquid-phase chromatographic column separation, and the part that benzo [α] pyrene goes out peak enters in gas chromatography system by the cutting of numerical control T-valve, and remainder enters waste liquid.The part that cutting enters gas chromatography is by the solid-phase extraction column of installing in injection port, and benzo [α] pyrene is adsorbed on solid-phase extraction column, and now post web member place enters mouthful closing of separating column, and solvent is discharged by solvent exhaust valve; After solid phase extraction concentration completes, with carrier gas, dry up the solvent on solid-phase extraction column, then close solvent exhaust valve, post web member place opens towards the mouth of capillary column simultaneously; Start gas chromatography intensification and carry out GC-MS analysis.In gas chromatographic analysis process, after gas chromatography heats up, be adsorbed on benzo [α] the pyrene gasification on solid-phase extraction column, by carrier gas, carried by capillary column separation, then through Mass Spectrometer Method, determine content.
The feature of this device is that on-line solid phase extraction post is placed in the injection port of gas chromatography, be connected by post web member with chromatographic column, post web member place has Numerical control valve can allow liquid phase solvent discharge, and after draining solvent, can close solvent exhaust valve again, enters gas chromatographic analysis.By numerical control T-valve, cut, the component to be measured that can allow needs after liquid chromatography separation enters gas chromatographic analysis, and unwanted other component enters waste liquid.
Compared with prior art, its beneficial effect is in the present invention:
1, the present invention is considering on the basis of prior art advantage, has developed a kind of gas chromatography-mass spectrum new equipment and method with on-line solid phase extraction, relies on new method and device thereof can realize the effective detection to benzo in cigarette mainstream flue gas [α] pyrene; Compare with the device of existing maturation, this device can fully be realized gas chromatography more volume sample introduction, sample for low content, can allow through liquid phase separation component repeatedly cumulative, after running up to desirable amount of analysis, proceed to again gas chromatographic analysis, when realizing sample high-efficient purification, greatly improved sensitivity for analysis;
2, the solvent of tradition liquid phase-gas phase chromatography in series is processed and is adopted vacuum solvent evaporation technique, shortcoming is not to be suitable for effumability composition, and not being suitable for one-level chromatogram is the moisture chromatogram mode of mobile phase (ion-exchange chromatography or reverse-phase chromatography), in order to overcome this shortcoming, we have designed " by Solid-Phase Extraction, processing the solvent in two-stage chromatogram ", the sample just dividing through one-level chromatogram enters the injection port of gas chromatography, by the solid-phase extraction column in injection port, determinand is adsorbed on solid-phase extraction column, mobile phase---solvent flows out from solvent exhaust valve, after drying up solid-phase extraction column with carrier gas, close solvent exhaust valve, start secondary stratographic analysis simultaneously.Because mobile phase is to flow through after solid-phase extraction column to flow out, do not need evaporating solvent, so liquid chromatography just minute can be used moisture Flow Injection Chemiluminescence Method phase;
3 compare with the chromatography in series of existing maturation, apparatus of the present invention can fully realize one-level chromatogram (LC) more volume sample introduction and one-level chromatographic fraction more volume incision secondary chromatogram (GC), sample for low content, can allow through liquid phase separation component repeatedly cumulative, after running up to desirable amount of analysis, proceed to again gas chromatographic analysis, when realizing sample high-efficient purification, greatly improved sensitivity for analysis.Rely on method that new equipment sets up for the analysis of cigarette smoke benzopyrene, and and the contrasting of the method for GB (GB T21130-2007), the results are shown in accompanying drawing 2.Compare with existing national standard method, adopt the method sensitivity of liquid phase-gas phase two dimension chromatogram to improve over more than 5 times; And assorted peak obviously reduces in chromatogram, interpret sample clean-up effect significantly improves; Because on-line operation has reduced transfer in sample preparation process and the loss of composition to be measured, the precision of sample analysis result is also greatly improved.
Accompanying drawing explanation
Fig. 1 is the structural representation of the gas chromatography-mass spectrography device with on-line solid phase extraction purification function of the present invention, 1-liquid chromatographic system wherein, 2-gas chromatography-mass spectrum system, 3-numerical control T-valve, 4-solid-phase extraction column, 5-pump, 6-injector, 7-chromatographic column, 8-detecting device, 9-solvent exhaust valve, 10-capillary separation column, 11-post web member;
Fig. 2 is for measuring the method for cigarette smoke benzo [α] pyrene and the gas chromatogram comparison diagram that GB T21130-2007 method records with the present invention with on-line solid phase extraction, wherein to be the present invention measure with on-line solid phase extraction the gas chromatogram that the method for cigarette smoke benzo [α] pyrene records to a figure, and b figure is the gas chromatogram that GB T21130-2007 method records.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated, but never in any form the present invention is limited, and any conversion or the replacement based on the present invention's requirement, done, all belong to protection scope of the present invention.
At present China's standard GB/T T21130-2007 adopt the method for " cyclohexane extracts, silica gel column chromatography purifies, GC-MS analyze " to measure benzo [α] pyrene in cigarette mainstream flue gas; Because the content of benzo [α] pyrene in every cigarette is only at the nanogram order of magnitude, national standard method needs repeatedly to shift in operating process, concentrated, and analytical error is larger; But also must be in a large number with an organic solvent, big for environment pollution.
Only with the mensuration of benzo in cigarette smoke [α] pyrene, the present invention will be further described below:
As shown in Figure 1, a kind of gas chromatography-mass spectrography device with on-line solid phase extraction purification function, it is characterized in that comprising liquid chromatographic system 1, gas chromatography-mass spectrum system 2, numerical control T-valve 3 and solid-phase extraction column 4, described liquid chromatographic system 1 comprises the pump 5 connecting successively, injector 6, chromatographic column 7 and detecting device 8, between described liquid chromatographic system 1 and gas chromatography-mass spectrum system 2, being provided with can be for the numerical control T-valve 3 of component cutting, the solid-phase extraction column 4 of being made by exotic material is housed in the injection port of gas chromatography-mass spectrum system 2, solid-phase extraction column 4 by post web member 11 respectively with solvent exhaust valve 9, capillary separation column 10 is connected.Wherein, described exotic material is a kind of in anti-phase exotic material, multi-walled carbon nano-tubes, NACF, polyacrylate clad material and functional mesoporous material.
Embodiment 1
With on-line solid phase extraction, measure the method for cigarette smoke benzo [α] pyrene, use said apparatus, comprise the steps:
(1) flue gas trapping: flue gas trapping is pressed the condition of GB/T 19609-2004, Cigarette is in relative humidity 55%, balance 48h under the condition that temperature is 20 ℃; Every mouthful of suction is spaced apart 60s, and suction time is 2s, and suction capacity is 34.7mL, aspirates 20 domestic Virginian-type cigarettes, with 92mm cambridge filter trapping flue gas TPM;
(2) sample extraction: have the cambridge filter of mainstream smoke total particulate matter to put into the band plug conical flask of 150mL trapping, accurately add tri-grades of inner mark solutions of people 1mL with transfer pipet, accurately add 40mL cyclohexane, ultrasonic concussion 40min, ultrasonic frequency 60%, cool to room temperature, for stratographic analysis; Wherein, in described, be designated as deuterated benzo [α] pyrene;
(3) liquid chromatography is separated: chromatographic column is C18 reverse-phase chromatographic column, 2.1 * 250mm, 3.5 μ m; 40 ℃ of column temperatures; Mobile phase is acetonitrile/water, 70/30%; Flow velocity 0.6mL/min; Sampling volume is 20 μ L; Sample enters into liquid chromatographic system, separated through liquid-phase chromatographic column separating column by pump transport flow, and the outflow component of 15-17min is cut in gas chromatography by numerical control T-valve, and remainder enters waste liquid;
(4) part that is cut into gas chromatography enters the injection port of gas chromatography, by the solid-phase extraction column in injection port, allow benzo [α] pyrene be adsorbed on solid-phase extraction column, mobile phase flows out from solvent exhaust valve, then with carrier gas, dry up the water on solid-phase extraction column, and close solvent exhaust valve;
(5) gas chromatography-mass spectrometry analysis: the complete rear startup GC-MS of enrichment, heat up and allow the gasification of benzo [α] pyrene and bring capillary separation column separation into by carrier gas, Mass Spectrometer Method is quantitative, and component to be measured goes out peak at 10min, and MS spectrum storehouse is NIST; Wherein, gas chromatography chromatographic column is HP-5 MS capillary chromatographic column, 0.25mm * 30m, 0.25 μ m; 280 ℃ of injector temperatures, Splitless injecting samples, carrier gas is helium, constant current flow 1.2mL/min; Chromatographic column heating schedule: 150 ℃ of initial temperatures, with 6 ℃/min, rise to 280 ℃, keep 20min; Mass detector condition is: electron bombardment ionization source; 230 ℃ of ion source temperatures, 280 ℃ of transmission line temperature, quality of scanning scope 50～400amu, sweep spacing 0.5s.
For 6 kinds of cigarette samples, the measurement result of benzo [α] pyrene is between 6.26-12.8ng/ props up, and the recovery is between 92-98%.
Embodiment 2
With on-line solid phase extraction, measure the method for cigarette smoke benzo [α] pyrene, use said apparatus, comprise the steps:
(1) flue gas trapping: flue gas trapping is pressed the condition of GB/T 19609-2004, Cigarette is in relative humidity 60%, balance 48h under the condition that temperature is 22 ℃; Every mouthful of suction is spaced apart 60s, and suction time is 2s, and suction capacity is 35mL, aspirates 20 external blended type cigarettes, with 44mm cambridge filter trapping flue gas TPM;
(2) sample extraction: have the cambridge filter of mainstream smoke total particulate matter to put into the band plug conical flask of 150mL trapping, accurately add tri-grades of inner mark solutions of people 1mL with transfer pipet, accurately add 40mL methylene chloride, ultrasonic concussion 30min, ultrasonic frequency 60%, cool to room temperature, for stratographic analysis; Wherein, in described, be designated as deuterated benzo [α] pyrene;
(3) liquid chromatography is separated: chromatographic column is C18 reverse-phase chromatographic column, 2.1 * 250mm, 3.5 μ m; 40 ℃ of column temperatures; Mobile phase is acetonitrile/water, 70/30%; Flow velocity 0.6mL/min; Sampling volume is 20 μ L; Sample enters into liquid chromatographic system, separated through liquid-phase chromatographic column separating column by pump transport flow, and the outflow component of 15-17min is cut in gas chromatography by numerical control T-valve, and remainder enters waste liquid;
(4) part that is cut into gas chromatography enters the injection port of gas chromatography, by the solid-phase extraction column in injection port, allow benzo [α] pyrene be adsorbed on solid-phase extraction column, mobile phase flows out from solvent exhaust valve, then with carrier gas, dry up the water on solid-phase extraction column, and close solvent exhaust valve;
(5) gas chromatography-mass spectrometry analysis: the complete rear startup GC-MS of enrichment, heat up and allow the gasification of benzo [α] pyrene and bring capillary separation column separation into by carrier gas, Mass Spectrometer Method is quantitative, and component to be measured goes out peak at 10min, and MS spectrum storehouse is NIST; Wherein, gas chromatography chromatographic column is HP-5 MS capillary chromatographic column, 0.25mm * 30m, 0.25 μ m; 280 ℃ of injector temperatures, Splitless injecting samples, carrier gas is helium, constant current flow 1.2mL/min; Chromatographic column heating schedule: 150 ℃ of initial temperatures, with 6 ℃/min, rise to 280 ℃, keep 20min; Mass detector condition is: electron bombardment ionization source; 230 ℃ of ion source temperatures, 280 ℃ of transmission line temperature, quality of scanning scope 50～400amu, sweep spacing 0.5s.
For 8 kinds of cigarette samples, the measurement result of benzo [α] pyrene is between 5.8-13.4ng/ props up, and the recovery is between 88-104%.
Embodiment 3
With on-line solid phase extraction, measure the method for cigarette smoke benzo [α] pyrene, use said apparatus, comprise the steps:
(1) flue gas trapping: flue gas trapping is pressed the condition of GB/T 19609-2004, Cigarette is in relative humidity 65%, balance 48h under the condition that temperature is 24 ℃; Every mouthful of suction is spaced apart 60s, and suction time is 2s, and suction capacity is 35.3mL, aspirates 20 external blended type cigarettes, with 92mm cambridge filter trapping flue gas TPM;
(2) sample extraction: have the cambridge filter of mainstream smoke total particulate matter to put into the band plug conical flask of 150mL trapping, accurately add tri-grades of inner mark solutions of people 1mL with transfer pipet, accurately add 40mL acetone, ultrasonic concussion 50min, ultrasonic frequency 60%, cool to room temperature, for stratographic analysis; Wherein, in described, be designated as deuterated benzo [α] pyrene;
(3) liquid chromatography is separated: chromatographic column is C18 reverse-phase chromatographic column, 2.1 * 250mm, 3.5 μ m; 40 ℃ of column temperatures; Mobile phase is acetonitrile/water, 70/30%; Flow velocity 0.6mL/min; Sampling volume is 20 μ L; Sample enters into liquid chromatographic system, separated through liquid-phase chromatographic column separating column by pump transport flow, and the outflow component of 15-17min is cut in gas chromatography by numerical control T-valve, and remainder enters waste liquid;
(4) part that is cut into gas chromatography enters the injection port of gas chromatography, by the solid-phase extraction column in injection port, allow benzo [α] pyrene be adsorbed on solid-phase extraction column, mobile phase flows out from solvent exhaust valve, then with carrier gas, dry up the water on solid-phase extraction column, and close solvent exhaust valve;
(5) gas chromatography-mass spectrometry analysis: the complete rear startup GC-MS of enrichment, heat up and allow the gasification of benzo [α] pyrene and bring capillary separation column separation into by carrier gas, Mass Spectrometer Method is quantitative, and component to be measured goes out peak at 10min, and MS spectrum storehouse is NIST; Wherein, gas chromatography chromatographic column is HP-5 MS capillary chromatographic column, 0.25mm * 30m, 0.25 μ m; 280 ℃ of injector temperatures, Splitless injecting samples, carrier gas is helium, constant current flow 1.2mL/min; Chromatographic column heating schedule: 150 ℃ of initial temperatures, with 6 ℃/min, rise to 280 ℃, keep 20min; Mass detector condition is: electron bombardment ionization source; 230 ℃ of ion source temperatures, 280 ℃ of transmission line temperature, quality of scanning scope 50～400amu, sweep spacing 0.5s.
For 10 kinds of cigarette samples, the measurement result of benzo [α] pyrene is between 3.6-12.8ng/ props up, and the recovery is between 92-106%.
Test example 1
Identical with embodiment 1, replicate determination under the same conditions 7 times (same batch processed), the relative standard deviation of 7 replicate determination results as calculated, the RSD that obtains benzo [α] pyrene is 1.8%; In addition with same program by traditional GB T21130-2007 method analyzing samples, the RSD that records benzo [α] pyrene is 3.2%, as shown in Figure 2, result shows that the test result precision of improving one's methods is obviously higher.Carried out recovery of standard addition experiment, the recovery of classic method is between 88-105% simultaneously, and the recovery of improving one's methods is between 96-101%, and the recovery of improving one's methods is obviously high.
Wherein, the recovery=(the instrument amount of recording/addition) * 100%.Because instrument also has certain error, measured value is large than addition likely, and cause the recovery to surpass 100%, as long as being generally no more than 110% just belongs to normal range.
By reference to the accompanying drawings embodiments of the present invention are explained in detail above, but the present invention is not limited to above-mentioned embodiment, in the ken possessing those of ordinary skills, can also under the prerequisite that does not depart from aim of the present invention, makes a variety of changes.
Claims (8)
1. the gas chromatography-mass spectrography device with on-line solid phase extraction purification function, it is characterized in that comprising liquid chromatographic system, gas chromatography-mass spectrum system, numerical control T-valve and solid-phase extraction column, described liquid chromatographic system comprises the pump connecting successively, injector, chromatographic column and detecting device, between described liquid chromatographic system and gas chromatography-mass spectrum system, being provided with can be for the numerical control T-valve of component cutting, the solid-phase extraction column of being made by exotic material is housed in the injection port of gas chromatography-mass spectrum system, solid-phase extraction column by post web member respectively with solvent exhaust valve, separating column is connected.
2. the gas chromatography-mass spectrography device with on-line solid phase extraction purification function according to claim 1, is characterized in that described exotic material is a kind of in anti-phase exotic material, multi-walled carbon nano-tubes, NACF, polyacrylate clad material and functional mesoporous material.
3. with on-line solid phase extraction, measure a method for cigarette smoke benzo [α] pyrene, right to use require 1 described in device, it is characterized in that comprising the steps:
A, sample collection and preparation: with filter disc, trap benzo [α] pyrene, the filter disc after trapping is added containing in interior target organic solvent, ultrasonic concussion 30～50min obtains sample;
B, analysis: the sample that steps A is made enters into liquid chromatographic separation system, separated through liquid-phase chromatographic column post by pump transport flow, the outflow component that contains benzo [α] pyrene is cut in gas chromatography by numerical control T-valve, and remainder enters waste collecting device; The part of incision gas chromatography, by the solid-phase extraction column in injection port, allows benzo [α] pyrene be adsorbed on solid-phase extraction column, and mobile phase flows out from solvent exhaust valve; The complete rear startup GC-MS of enrichment, heats up and allows the gasification of benzo [α] pyrene and bring capillary separation column separation into by carrier gas, and Mass Spectrometer Method is quantitative.
4. the method for measuring cigarette smoke benzo [α] pyrene with on-line solid phase extraction according to claim 3, is characterized in that the filter disc described in steps A is 92mm cambridge filter or 44mm cambridge filter.
5. the method for measuring cigarette smoke benzo [α] pyrene with on-line solid phase extraction according to claim 3, is characterized in that organic solvent described in steps A is a kind of in cyclohexane, methylene chloride and acetone.
6. the method for measuring cigarette smoke benzo [α] pyrene with on-line solid phase extraction according to claim 3, is characterized in that the mobile phase A in mutually by pump transport flow described in step B is a kind of in acetonitrile-water, acetonitrile, first alcohol and water.
7. the method for measuring cigarette smoke benzo [α] pyrene with on-line solid phase extraction according to claim 3, is characterized in that the Mobile phase B in is mutually a kind of in water, methyl alcohol and ethanol to step B by pump transport flow.
8. the method for measuring cigarette smoke benzo [α] pyrene with on-line solid phase extraction according to claim 3, is characterized in that comprising the steps:
(1) flue gas trapping: flue gas trapping is pressed the condition of GB/T 19609-2004, Cigarette is in relative humidity 60 ± 5%, balance 48h under the condition that temperature is 22 ± 2 ℃; Every mouthful of suction is spaced apart 60s, and suction time is 2s, and suction capacity is 35 ± 0.3mL, aspirates 20 cigarette, with 92mm cambridge filter trapping flue gas TPM;
(2) sample extraction: have the cambridge filter of mainstream smoke total particulate matter to put into the band plug conical flask of 150mL trapping, accurately add tri-grades of inner mark solutions of people 1mL with transfer pipet, and add 40mL cyclohexane, ultrasonic concussion 40min; Wherein, in described, be designated as deuterated benzo [α] pyrene;
(3) liquid chromatography is separated: chromatographic column is C18 reverse-phase chromatographic column, 2.1 * 250mm, 3.5 μ m; 40 ℃ of column temperatures; Mobile phase is acetonitrile/water, 70/30%; Flow velocity 0.6mL/min; Sampling volume is 20 μ L; Sample enters into liquid chromatographic system, separated through liquid-phase chromatographic column separating column by pump transport flow, and the outflow component that contains benzo [α] pyrene is cut in gas chromatography by numerical control T-valve, and remainder enters waste liquid;
(4) part that is cut into gas chromatography enters the injection port of gas chromatography, by the solid-phase extraction column in injection port, allow benzo [α] pyrene be adsorbed on solid-phase extraction column, mobile phase flows out from solvent exhaust valve, then with carrier gas, dry up the water on solid-phase extraction column, and close solvent exhaust valve;
(5) gas chromatography-mass spectrometry analysis: the complete rear startup GC-MS of enrichment, heat up and allow the gasification of benzo [α] pyrene and bring capillary separation column separation into by carrier gas, Mass Spectrometer Method is quantitative; Wherein, gas chromatography chromatographic column is HP-5 MS capillary chromatographic column, 0.25mm * 30m, 0.25 μ m; 280 ℃ of injector temperatures, Splitless injecting samples, carrier gas is helium, constant current flow 1.2mL/min; Chromatographic column heating schedule: 150 ℃ of initial temperatures, with 6 ℃/min, rise to 280 ℃, keep 20min; Mass detector condition is: electron bombardment ionization source; 230 ℃ of ion source temperatures, 280 ℃ of transmission line temperature, quality of scanning scope 50～400amu, sweep spacing 0.5s.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104569253A (en) * | 2014-12-16 | 2015-04-29 | 国家烟草质量监督检验中心 | Method for determining benzo[a]pyrene in cigarette mainstream smoke |
| CN105403645A (en) * | 2015-12-22 | 2016-03-16 | 云南中烟工业有限责任公司 | On-line concentration device and application thereof to liquid phase-gas phase |
| CN105510465A (en) * | 2015-12-14 | 2016-04-20 | 云南中烟工业有限责任公司 | Gas chromatographic analysis device and analysis method capable of greatly improving analysis sensitivity |
| CN107656002A (en) * | 2016-07-26 | 2018-02-02 | 上海烟草集团有限责任公司 | Large volume sample injection technology and its application on a kind of gas chromatographic column |
| CN108375641A (en) * | 2018-05-29 | 2018-08-07 | 云南中烟工业有限责任公司 | The detection method of benzo [a] pyrene in a kind of tobacco leaf flue gas |
| CN108469475A (en) * | 2018-02-12 | 2018-08-31 | 云南中烟工业有限责任公司 | A kind of method of benzo [a] pyrene in measurement cigarette mainstream flue gas |
| CN109212010A (en) * | 2018-09-05 | 2019-01-15 | 东南大学 | A kind of sample detection methods of simplicity fast high-flux |
| CN109828050A (en) * | 2019-03-08 | 2019-05-31 | 中钢集团鞍山热能研究院有限公司 | A kind of method of 3,4- BaP content in quick measurement coal tar, coal tar pitch |
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| US10849600B2 (en) | 2016-03-08 | 2020-12-01 | Entech Instruments Inc. | Breath condensate and saliva analysis using oral rinse |
| CN113214603A (en) * | 2021-05-12 | 2021-08-06 | 云南中烟工业有限责任公司 | Carbon nanotube epoxy resin composite material electrode, preparation method and application thereof |
| CN113970601A (en) * | 2020-07-23 | 2022-01-25 | 湖南中烟工业有限责任公司 | On-line analysis and detection device and method for smoke of heated cigarette |
| US11896366B2 (en) | 2018-03-06 | 2024-02-13 | Entech Instruments Inc. | Ventilator-coupled sampling device and method |
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| CN104569253B (en) * | 2014-12-16 | 2016-03-23 | 国家烟草质量监督检验中心 | The assay method of benzo [a] pyrene in a kind of cigarette mainstream flue gas |
| CN104569253A (en) * | 2014-12-16 | 2015-04-29 | 国家烟草质量监督检验中心 | Method for determining benzo[a]pyrene in cigarette mainstream smoke |
| CN105510465A (en) * | 2015-12-14 | 2016-04-20 | 云南中烟工业有限责任公司 | Gas chromatographic analysis device and analysis method capable of greatly improving analysis sensitivity |
| CN105403645A (en) * | 2015-12-22 | 2016-03-16 | 云南中烟工业有限责任公司 | On-line concentration device and application thereof to liquid phase-gas phase |
| US10849600B2 (en) | 2016-03-08 | 2020-12-01 | Entech Instruments Inc. | Breath condensate and saliva analysis using oral rinse |
| US10502664B2 (en) | 2016-03-08 | 2019-12-10 | Entech Instruments Inc. | Vacuum-assisted sample extraction device and method |
| CN107656002B (en) * | 2016-07-26 | 2020-04-14 | 上海烟草集团有限责任公司 | Large-volume sample introduction technology on gas chromatography column and application thereof |
| CN107656002A (en) * | 2016-07-26 | 2018-02-02 | 上海烟草集团有限责任公司 | Large volume sample injection technology and its application on a kind of gas chromatographic column |
| CN108469475A (en) * | 2018-02-12 | 2018-08-31 | 云南中烟工业有限责任公司 | A kind of method of benzo [a] pyrene in measurement cigarette mainstream flue gas |
| US11896366B2 (en) | 2018-03-06 | 2024-02-13 | Entech Instruments Inc. | Ventilator-coupled sampling device and method |
| CN108375641B (en) * | 2018-05-29 | 2021-02-09 | 云南中烟工业有限责任公司 | Method for detecting benzo [ a ] pyrene in tobacco smoke |
| CN108375641A (en) * | 2018-05-29 | 2018-08-07 | 云南中烟工业有限责任公司 | The detection method of benzo [a] pyrene in a kind of tobacco leaf flue gas |
| CN109212010A (en) * | 2018-09-05 | 2019-01-15 | 东南大学 | A kind of sample detection methods of simplicity fast high-flux |
| CN109828050A (en) * | 2019-03-08 | 2019-05-31 | 中钢集团鞍山热能研究院有限公司 | A kind of method of 3,4- BaP content in quick measurement coal tar, coal tar pitch |
| CN113970601A (en) * | 2020-07-23 | 2022-01-25 | 湖南中烟工业有限责任公司 | On-line analysis and detection device and method for smoke of heated cigarette |
| CN113214603A (en) * | 2021-05-12 | 2021-08-06 | 云南中烟工业有限责任公司 | Carbon nanotube epoxy resin composite material electrode, preparation method and application thereof |
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