CN105572285A - Method for measuring semi-volatile substances in mainstream smoke of cigarettes - Google Patents
Method for measuring semi-volatile substances in mainstream smoke of cigarettes Download PDFInfo
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- CN105572285A CN105572285A CN201511010394.XA CN201511010394A CN105572285A CN 105572285 A CN105572285 A CN 105572285A CN 201511010394 A CN201511010394 A CN 201511010394A CN 105572285 A CN105572285 A CN 105572285A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
Abstract
The invention discloses a method for measuring semi-volatile substances in mainstream smoke of cigarettes, and in particular relates to a chromatography-tandem mass spectrometry based method for determining contents of three semi-volatile substances, pyridine, styrene and quinoline, in the mainstream smoke of cigarettes. The method includes preparation an internal standard solution, a standard solution and a sample solution, analysis by gas chromatography-tandem mass spectrometry, and calculation of measured results. The method uses the respective deuterated substances of the objects as the internal standard substances for quantification, has the advantages of simpleness, sensitive response and accurate quantitative analysis, and effectively reduces the interference caused by the complex matrix of a sample. The conditions of the employed analytical instrument endow good signal response on the objects, and have good linear correlation. The method has high sensitivity and good reproducibility and recovery, and is applicable to quantitative analysis of trace objects in complex matrices of mainstream smoke.
Description
Technical field
The present invention relates to a kind of method measuring half volatile material in cigarette mainstream flue gas, belong to cigarette physical and chemical index detection technique field.
Background technology
Half volatile material is the important component part of cigarette smoke, all distribution is had in total particulate matter in mainstream smoke and gas gas-phase objects, wherein pyridine, styrene and quinoline are semi-volatile organic compounds of greatest concern, are the important chemical compositions that Hoffman inventory and Canadian government detect in list.In addition, one of concern chemical composition of pyridine, styrene and quinoline or Environmental Protection Agency (EPA) defined, Canadian government also using these three kinds of materials as tobacco product control composition and the chemical composition that must disclose content.Along with people are to the enforcement of deep and " Framework Convention on Tobacco Control " of these compounds poison rational knowledge in flue gas, estimate in the near future, many countries limit by working out relevant laws and regulations to the burst size of pyridine in cigarette mainstream flue gas, styrene and quinoline, and disclose the burst size of these compounds in cigarette mainstream flue gas.Therefore, set up and formulate the assay method of these half volatile materials in a kind of reproducible, cigarette mainstream flue gas that stability is high, this fulfils situation needs of tobacco framework convention to adapting to China, and safely etc. aspect is all significant to monitor the burst size of these materials and guarantee health of human body.
At present, many countries all establish the assay method of these compounds, comprise cold solvent absorption process, thermal desorption method and adsorbent method etc.Half volatile material all has distribution in the granule phase substance and gas gas-phase objects of cigarette mainstream flue gas, so traditional filter disc and Electrostatic method all can not trap these semi-volatile organic compounds in flue gas completely effectively.Document in the past mainly adopts the semi-volatility component in cambridge filter trapping flue gas grain phase, cryotrap trapping flue gas gas phase, and then adopt gas chromatography-mass spectrum to detect, the method is also by Canadian government method is adopted.But in the method, in order to effectively trap the semi-volatility component in gaseous phase of main stream smoke of cigarette thing, often needing is together in series the solvent bottle of two sub-cooled (≤-70 DEG C) traps, this device dead volume is larger, need to use dry ice to cool, operate the volatile organic compounds in very loaded down with trivial details Shanghai Tobacco company employing thermal desorption technology and GC/MS method mensuration cigarette smoke, the method has good sensitivity.But there is many problems, such as Smoke Particulate produces cold-trap (thermal desorption instrument critical component) and pollutes, solvent extraction and gas chromatography mass spectrometry method can only be adopted to analyze, flue gas gas gas-phase objects then adopts thermal desorption-GC-MS(gas chromatography-mass spectrography) to measure, secondly, thermal desorption method stability is bad, and needs to set multiple parameter to thermal desorption instrument, and adsorption sampling pipe is larger on the resistance to suction impact in smoking experiment.Generally speaking, existing analytical approach mainly adopts gas chromatograph-mass spectrometer (GCMS) (GC-MS) to analyze.But, when using GC-MS to analyze, by the impact of flue gas complex matrices, be limited to the level that in flue gas, half volatile substance content is lower, wherein the deuterated internal standard compound of pyridine and quinoline easily and interfering material flow out altogether, cause the object recovery on the low side, and then impact brought on accurate quantitative analysis.
At present, gas chromatography tandem mass spectrometry (GC-MS/MS) is a kind of instrument for Determination of Trace Volatile in complex matrices and semi-volatile organic compounds qualitative and quantitative analysis, is applied to more and more widely in Research of Environmental Sciences's work.Because its baseline noise goes to zero, therefore there is higher sensitivity and lower detection limit, effectively can increase the selectivity that object to be measured in complex matrices is detected, to extreme trace analysis, there is higher reliability, be used to the mensuration of the compositions such as the residues of pesticides in the matrix such as biological sample, water, olive oil, flue gas, palycyclic aromatic, nitrosamine.For this reason, this patent adopts GC-MS/MS to carry out quantitative analysis to trace in cigarette smoke half volatile substance pyridine, styrene and quinoline first.
Summary of the invention
The present invention is intended to overcome existing technological deficiency, a kind of method adopting gas chromatography tandem mass spectrometry instrument to measure half volatile substance pyridine, styrene and quinoline release content in cigarette mainstream flue gas is provided, quick, the accurate content detecting half volatile substance pyridine, styrene and quinoline in cigarette mainstream flue gas of the method energy, measurement result is accurate, highly sensitive, and matrix interference is few.
Specifically, present invention employs following technical scheme:
Measure a method for half volatile material in cigarette mainstream flue gas, it is characterized in that, said method comprising the steps of:
(1) preparation of inner mark solution: with D5-pyridine, D8-styrene and D7-quinoline for internal standard compound, use absorbent solution is solvent, prepares inner mark solution, wherein said absorbent solution to be volumetric concentration be 1% ammoniacal liquor-methanol solution;
(2) preparation of standard working solution: with pyridine, styrene and quinoline standard items for object, use absorbent solution is solvent, be prepared into Standard Stock solutions through stepwise dilution, then add a certain amount of inner mark solution respectively, be prepared into standard working solution;
(3) preparation of sample solution: gather the object in cigarette smoke, accurately adds the absorbent solution of a certain amount of inner mark solution and certain volume, mechanical shaking extraction, and scavenging solution obtains sample solution after crossing organic filter membrane;
(4) gas chromatography tandem mass spectrometry instrument is analyzed: carry out detection with gas chromatography tandem mass spectrometry instrument (GC-MS/MS) to standard working solution and sample solution and analyze;
(5) drafting of standard working curve and the calculating of sample result.
In above method, the preparation of described inner mark solution comprises the following steps:
(1) mark storing solution in: accurately take 0.1gD5-pyridine, 0.05gD8-styrene and 0.005gD7-quinoline, be accurate to 0.1mg, in the volumetric flask of 100mL, dissolve by absorbent solution and be settled to scale;
(2) inner mark solution: accurately pipette mark storing solution in 0.4mL, in the volumetric flask of 100mL, dilute by absorbent solution and be settled to scale.
Further, the preparation of described standard working solution comprises the following steps:
(1) primary standard storing solution: accurately take 0.5g pyridine, 0.25g styrene and 0.025g quinoline, be accurate to 0.1mg, in the volumetric flask of 100mL, dissolves by absorbent solution and is settled to scale;
(2) secondary standard storing solution: accurately pipette 2mL primary standard storing solution, in the volumetric flask of 100mL, dilutes by absorbent solution and is settled to scale;
(3) standard working solution: accurately pipette secondary standard storing solution 10 μ L, 40 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L respectively, to in the volumetric flask of 10mL, accurately add 500 μ L inner mark solutions more respectively, be settled to scale with diluted absorption solution, obtain series standard working solution.
In addition, the preparation of described sample solution comprises the following steps:
(1) cigarette smoking: aspirate 20 cigarette according to the requirement of GB/T19609 standard, wherein with the granule phase substance in cambridge filter trapping cigarette mainstream flue gas, and be positioned over the gas gas-phase objects filled in the absorption bottle trapping cigarette mainstream flue gas of 20mL absorbent solution in ice cube/aqueous mixtures with 1;
(2) sample solution: the trapping that above step obtains had the cambridge filter of TPM to be positioned in 250mL conical flask, wherein filter disc answers full wafer to put into conical flask to pave, can not shred or tear up, and trapping has the absorbent solution of gas gas-phase objects to be all transferred in conical flask, and with 20mL absorbent solution washing absorption bottle several times, cleansing solution is transferred to conical flask in the lump, finally add 400 μ L inner mark solutions again, conical flask is placed in oscillator and extracts 30min under 160r/min condition, leave standstill a moment, get 2mL extract, use 0.45 μm of organic phase membrane filtration, obtain sample solution.
Wherein, described GC-MS/MS analyzes, and its instrumental conditions is: the DB-WAX capillary chromatographic column adopting 30m × 0.25mm × 0.25 μm specification; Carrier gas is helium, and constant current speed is 1.2mL/min; Input mode: sample size is 1 μ L, split sampling, and split ratio is 10:1; Injector temperature is 250 DEG C; Transmission line temperature is 280 DEG C; Heating schedule is initial temperature is 50 DEG C, is increased to 80 DEG C, then is increased to 240 DEG C with the speed of 10 DEG C/min with the speed of 2 DEG C/min, keeps 5min,
Its mass spectrophotometry condition is: ionization mode is EI source, positive ion mode; Ion source temperature: 230 DEG C; Quadrupole rod temperature: be 150 DEG C; Collision gas: nitrogen, flow velocity 1.5mL/min, carrier gas helium flow velocity is 2.25mL/min; Multiple-reaction monitoring MRM pattern, detail parameters is listed in the table below:
The MRM parameter list of object
| Compound | Parent ion | Product ion | Collision energy eV |
| Pyridine | 79 | 52 | 15 |
| D5-pyridine | 84 | 56 | 20 |
| Styrene | 104 | 78 | 15 |
| D8-styrene | 112 | 84 | 15 |
| Quinoline | 129 | 102 | 20 |
。
Further in above method, described Specification Curve of Increasing and result are calculated as follows: with the ratio of the deuterated interior target concentration with it of object in standard working solution for horizontal ordinate, with the ratio of the deuterated interior target peak area with it of object in chromatogram for ordinate, carry out linear regression analysis, obtain standard working curve, by object in the sample solution that records under the same terms with it deuterated interior target chromatographic peak area ratio, substitute into standard working curve, try to achieve the content of object in cigarette sample according to following formula:
In formula:
W---the content of 3 kinds of half volatile materials in cigarette sample, unit is that microgram is often propped up, and μ g/ props up;
A---the peak area of 3 kinds of half volatile materials;
As---target peak area in corresponding;
The intercept of b---standard working curve;
Ms---target quality in adding, unit is microgram, μ g;
The slope of a---standard working curve;
The quantity of M---cigarette, unit is for propping up.
Beneficial effect: detection method of the present invention is optimized confirmation to sample treatment and chromatograph mass spectrum analysis condition.Compared with prior art, the present invention has following excellent results:
(1) the inventive method measures the content of half volatile material pyridine, styrene and quinoline in cigarette mainstream flue gas first based on gas chromatography tandem mass spectrometry instrument, solving half volatile substance release water gaging in flue gas puts down low, and the impact of the factor such as the Analysis interference of flue gas complex matrices on object be serious.
(2) the inventive method utilizes inner mark method ration, can accurate constant volume, and can reduce the error brought by pre-treating method reappearance and instrument precision problem.
(3) the inventive method have selected peak shape and the best DB-WAX post of separating effect is separating column, and adopt the GC-MS/MS (MRM) that simultaneously can provide quantitative and qualitative analysis information as detecting pattern, improve the sensitivity of response signal, ensure that precision of analysis.
(4) the inventive method uses 1 gas gas-phase objects filled in absorption bottle (being positioned in ice cube/aqueous mixtures) the trapping cigarette mainstream flue gas of 20mL absorbent solution first, both ensure that the arresting efficiency of object, and has made again operation more easy.
(5) the present invention adopts object deuterated thing to be separately that internal standard compound carries out quantitatively, easy and simple to handle, respond sensitive, quantitative test is accurate, effectively reduce the interference brought because sample substrate is complicated, the analytical instrument condition adopted makes object have good signal response, and there is good linear dependence, the detection limit of 3 kinds of half volatile materials is respectively 10.63ng/ and props up, 2.61ng/ props up and props up with 4.52ng/, repeatability (RSD) is respectively 1.28%, 2.91% and 5.67%, recovery of standard addition is respectively 93.04% ~ 97.94%, 85.61% ~ 94.17%, and between 89.68% ~ 92.59%, the highly sensitive of this method is described, repeatability and the recovery better, be suitable for the quantitative test of trace object in flue gas complex matrices.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of assay method of the present invention;
Fig. 2 is the Ion-pair chromalography figure of half volatile material pyridine, styrene and quinoline in standard working solution;
Fig. 3 is the Ion-pair chromalography figure of half volatile material pyridine, styrene and quinoline in sample solution.
Embodiment
The object of the present invention is to provide a kind of quick, sensitive and measure the method for half volatile substance pyridine, styrene and quinoline release content in cigarette mainstream flue gas exactly, method of the present invention is a kind of method measuring half volatile material in cigarette mainstream flue gas based on gas chromatography-tandem mass spectrometer, comprises the following steps:
(1) preparation of inner mark solution: with D5-pyridine, D8-styrene and D7-quinoline for internal standard compound, use volumetric concentration be 1% ammoniacal liquor-methanol solution (hereinafter referred to as absorbent solution) be solvent, prepare inner mark solution.
(2) preparation of standard working solution: with pyridine, styrene and quinoline standard items for object, use absorbent solution is solvent, be prepared into Standard Stock solutions through stepwise dilution, then add a certain amount of inner mark solution respectively, be prepared into standard working solution.
(3) preparation of sample solution: gather the object in cigarette smoke, accurately adds the absorbent solution of a certain amount of inner mark solution and certain volume, mechanical shaking extraction, and scavenging solution obtains sample solution after crossing organic filter membrane.
(4) gas chromatography tandem mass spectrometry instrument is analyzed: carry out detection with gas chromatography tandem mass spectrometry instrument (GC-MS/MS) to standard working solution and sample solution and analyze.
(5) drafting of standard working curve and the calculating of sample result.
The preparation of described inner mark solution, specifically comprise the following steps: mark storing solution in (1): accurately take 0.1gD5-pyridine, 0.05gD8-styrene and 0.005gD7-quinoline, be accurate to 0.1mg, in the volumetric flask of 100mL, dissolve by absorbent solution and be settled to scale.(2) inner mark solution: accurately pipette mark storing solution in 0.4mL, in the volumetric flask of 100mL, dilute by absorbent solution and be settled to scale.
The preparation of described standard working solution, specifically comprise the following steps: (1) primary standard storing solution: accurately take 0.5g pyridine, 0.25g styrene and 0.025g quinoline, be accurate to 0.1mg, in the volumetric flask of 100mL, dissolve by absorbent solution and be settled to scale.(2) secondary standard storing solution: accurately pipette 2mL primary standard storing solution, in the volumetric flask of 100mL, dilutes by absorbent solution and is settled to scale.(3) standard working solution: accurately pipette secondary standard storing solution 10 μ L, 40 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L respectively, to in the volumetric flask of 10mL, accurately add 100 μ L inner mark solutions more respectively, be settled to scale with diluted absorption solution, obtain series standard working solution.
The preparation of described sample solution, specifically comprise the following steps: (1) cigarette smoking: aspirate 20 cigarette according to the requirement of GB/T19609 standard, wherein with the granule phase substance in cambridge filter trapping cigarette mainstream flue gas, and fill the gas gas-phase objects in absorption bottle (being positioned in ice cube/aqueous mixtures) the trapping cigarette mainstream flue gas of 20mL absorbent solution with 1.(2) sample solution: (filter disc is answered full wafer to put into conical flask and paved the trapping that upper step obtains to be had the cambridge filter of TPM to be positioned in 250mL conical flask, can not shred or tear up), and trapping has the absorbent solution of gas gas-phase objects to be all transferred in conical flask, and with 20mL absorbent solution washing absorption bottle several times, cleansing solution is transferred to conical flask in the lump, finally adds 400 μ L inner mark solutions again.Conical flask is placed in oscillator and extracts 30min under 160r/min condition, leave standstill a moment.Get 2mL extract, use 0.45 μm of organic phase membrane filtration, obtain sample solution.
Described GC-MS/MS analyzes, and its instrumental conditions is: adopt DB-WAX (30m × 0.25mm × 0.25 μm) capillary chromatographic column; Carrier gas is helium, and constant current speed is 1.2mL/min; Input mode: sample size is 1 μ L, split sampling, and split ratio is 10:1; Injector temperature is 250 DEG C; Transmission line temperature is 280 DEG C; Heating schedule is initial temperature is 50 DEG C, is increased to 80 DEG C, then is increased to 240 DEG C with the speed of 10 DEG C/min with the speed of 2 DEG C/min, keeps 5min.Its mass spectrophotometry condition is: ionization mode is EI source, positive ion mode; Ion source temperature: 230 DEG C; Quadrupole rod temperature: be 150 DEG C; Collision gas: nitrogen, flow velocity 1.5mL/min, carrier gas (helium) flow velocity is 2.25mL/min; Multiple-reaction monitoring (MRM) pattern, detail parameters is listed in the table below.
The MRM parameter list of object
Described Specification Curve of Increasing and result are calculated as follows: with the ratio of the deuterated interior target concentration with it of object in standard working solution for horizontal ordinate, with the ratio of the deuterated interior target peak area with it of object in chromatogram for ordinate, carry out linear regression analysis, obtain standard working curve.By object in the sample solution that records under the same terms with it deuterated interior target chromatographic peak area ratio, substitute into standard working curve, try to achieve the content of object in cigarette sample according to following formula.
In formula:
W---the content of 3 kinds of half volatile materials in cigarette sample, unit is that microgram is often propped up (μ g/ props up);
A---the peak area of 3 kinds of half volatile materials;
As---target peak area in corresponding;
The intercept of b---standard working curve;
Ms---target quality in adding, unit is microgram (μ g);
The slope of a---standard working curve;
The quantity of M---cigarette, unit is for propping up.
Below the present invention will be described in more detail in conjunction with specific embodiments again.
Embodiment 1
The present embodiment is to the detection method of half volatile material pyridine, styrene and quinoline in cigarette mainstream flue gas following (process flow diagram of described detection method is as shown in Figure 1):
(1) preparation of inner mark solution
1. mark storing solution in: accurately take 0.1011gD5-pyridine, 0.0515gD8-styrene and 0.0052gD7-quinoline, in the volumetric flask of 100mL, be the ammoniacal liquor-dissolve with methanol solution of 1% by volumetric concentration and be settled to scale.2. inner mark solution: accurately pipette mark storing solution in 0.4mL, in the volumetric flask of 100mL, dilute with ammoniacal liquor-methanol solution that volumetric concentration is 1% and be settled to scale.Wherein the concentration of D5-pyridine, D8-styrene and D7-quinoline is respectively 4.044 μ g/mL, 2.06 μ g/mL and 0.208 μ g/mL.
(2) preparation of standard working solution
1. primary standard storing solution: accurately take 0.5172g pyridine, 0.2521g styrene and 0.0252g quinoline, be accurate to 0.1mg, in the volumetric flask of 100mL, dissolves by absorbent solution and is settled to scale.2. secondary standard storing solution: accurately pipette 2mL primary standard storing solution, in the volumetric flask of 100mL, dilutes by absorbent solution and is settled to scale.3. standard working solution: accurately pipette secondary standard storing solution 10 μ L, 40 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L respectively, to in the volumetric flask of 10mL, accurately add 500 μ L inner mark solutions more respectively, scale is settled to diluted absorption solution, obtain series standard working solution, wherein the concentration range of pyridine, styrene and quinoline is respectively 0.10344 ~ 10.344 μ g/mL, 0.05042 ~ 5.042 μ g/mL and 0.00504 ~ 0.504 μ g/mL.
(3) preparation of sample solution
1. cigarette smoking: with city's pin cigarette for object, 20 cigarette are aspirated according to the requirement of GB/T19609 standard, wherein with the granule phase substance in 92mm cambridge filter trapping cigarette mainstream flue gas, and fill the gas gas-phase objects in absorption bottle (being positioned in ice cube/aqueous mixtures) the trapping cigarette mainstream flue gas of 20mL absorbent solution with 1.2. sample solution: (filter disc is answered full wafer to put into conical flask and paved the trapping that upper step obtains to be had the cambridge filter of TPM to be positioned in 250mL conical flask, can not shred or tear up), and trapping has the absorbent solution of gas gas-phase objects to be all transferred in conical flask, and with 20mL absorbent solution washing absorption bottle several times, cleansing solution is transferred to conical flask in the lump, finally adds 400 μ L inner mark solutions again.Conical flask is placed in oscillator and extracts 30min under 160r/min condition, leave standstill a moment.Get 2mL extract, use 0.45 μm of organic phase membrane filtration, obtain sample solution.
(4) gas chromatography tandem mass spectrometry analysis
Standard working solution and the sample solution to be measured of getting 6 variable concentrations respectively carry out gas chromatography tandem mass spectrometry analysis (in described standard working solution, sample solution, the chromatogram of object and internal standard compound as shown in Figure 2 to 3).
Its instrumental conditions is: adopt DB-WAX (30m × 0.25mm × 0.25 μm) capillary chromatographic column; Carrier gas is helium, and constant current speed is 1.2mL/min; Input mode: sample size is 1 μ L, split sampling, and split ratio is 10:1; Injector temperature is 250 DEG C; Transmission line temperature is 280 DEG C; Heating schedule is initial temperature is 50 DEG C, is increased to 80 DEG C, then is increased to 240 DEG C with the speed of 10 DEG C/min with the speed of 2 DEG C/min, keeps 5min.Its mass spectrophotometry condition is: ionization mode is EI source, positive ion mode; Ion source temperature: 230 DEG C; Quadrupole rod temperature: be 150 DEG C; Collision gas: nitrogen, flow velocity 1.5mL/min, carrier gas (helium) flow velocity is 2.25mL/min; Multiple-reaction monitoring (MRM) pattern, detail parameters is listed in the table below 1.
The MRM parameter list of table 1 object
(5) Specification Curve of Increasing and result calculate
First, with the ratio of the deuterated interior target concentration with it of object in standard working solution for horizontal ordinate, with the ratio of the deuterated interior target peak area with it of object in chromatogram for ordinate, carry out linear regression analysis, obtain standard working curve.Get the standard working solution of least concentration, do 9 Parallel testing analyses, calculate its standard deviation, with the concentration that the standard deviation of 3 times is corresponding, the detection limit of the method that draws that converts.The data such as the regression equation corresponding with standard working curve, related coefficient, detection limit see the following form 2.
The working curve of table 2 analytical approach and detection limit
| Compound | Concentration range (μ g/mL) | Regression equation | Related coefficient | Detection limit (ng/ props up) |
| Pyridine | 0.10344－10.344 | Y＝1.115X-0.1238 | 0.99956 | 10.63 |
| Styrene | 0.05042－5.042 | Y＝1.150X-0.1397 | 0.99963 | 2.61 |
| Quinoline | 0.00504－0.504 | Y＝1.272X-0.09409 | 0.99941 | 4.52 |
Then, by object in the sample solution that records under the same terms with it deuterated interior target chromatographic peak area ratio, substitute into standard working curve, try to achieve the content of object in cigarette sample according to following formula.
In formula:
W---the content of 3 kinds of half volatile materials in cigarette sample, unit is that microgram is often propped up (μ g/ props up);
A---the peak area of 3 kinds of half volatile materials;
As---target peak area in corresponding;
The intercept of b---standard working curve;
Ms---target quality in adding, unit is microgram (μ g);
The slope of a---standard working curve;
The quantity of M---cigarette, unit is for propping up.
In the present embodiment, in 10 different brands cigarette samples, half volatile material pyridine, styrene and isoquinoline level testing result see the following form 3:
Table 3 cigarette sample testing result (μ g/ props up)
| Cigarette sample | Pyridine | Styrene | Quinoline |
| Virginian-type cigarette 1 | 3.85 | 4.97 | 0.26 |
| Virginian-type cigarette 2 | 2.80 | 3.97 | 0.24 |
| Virginian-type cigarette 3 | 5.82 | 7.36 | 0.33 |
| Virginian-type cigarette 4 | 4.75 | 7.55 | 0.18 |
| Virginian-type cigarette 5 | 8.78 | 8.98 | 0.31 |
| Virginian-type cigarette 6 | 14.17 | 11.25 | 0.53 |
| Blended type cigarette 1 | 8.40 | 9.00 | 0.48 |
| Blended type cigarette 2 | 21.27 | 14.76 | 0.59 |
| Blended type cigarette 3 | 5.42 | 6.29 | 0.19 |
| Blended type cigarette 4 | 5.99 | 6.58 | 0.42 |
Embodiment 2
The detection method of the present embodiment to precision of the present invention and recovery of standard addition is as follows:
With a cigarette sample for analytic target, carry out withinday precision experiment respectively, withinday precision experiment is same sample replicate determination 6 times (same batch processed) under identical conditions, calculate the relative standard deviation (RSD) of 6 parallel determinations respectively, measurement result sees the following form 4.Result display in table, the RSD<6% of the in a few days repeatability of this experimental technique, for the quantitative test of micro substance, shows that method has good precision.
The precision result of table 4 method
With replica test cigarette sample used for analytic target, cigarette is normally aspirated, after suction, process according to above-mentioned sample-pretreating method, add the semi-volatile compounds mixed sample of suitable basic, normal, high three different contents of its burst size, carry out the test of matrix mark-on, the results are shown in following table 5.As can be seen from the table, the recovery of standard addition of sample is between 85.61% ~ 97.94%, and illustration method has good accuracy.
The recovery of standard addition result of table 5 method
Standard solution used by the present embodiment is only described for one of them concentration, the typical curve that standard solution prepared by other concentration value obtains through the analysis of gas chromatography tandem mass spectrometry instrument and regression equation same as the previously described embodiments, do not enumerating at this.Illustrated embodiment just method for a better understanding of the present invention, do not have any restriction, namely the method for said method or equivalent above-mentioned situation is all included in the protection domain of technical scheme of the present invention.
With embodiment, embodiments of the present invention are described in detail by reference to the accompanying drawings above, but the invention is not restricted to above-mentioned embodiment, in the ken that art those of ordinary skill possesses, can also make a variety of changes under the prerequisite not departing from present inventive concept.
Claims (6)
1. measure a method for half volatile material in cigarette mainstream flue gas, it is characterized in that, said method comprising the steps of:
(1) preparation of inner mark solution: with D5-pyridine, D8-styrene and D7-quinoline for internal standard compound, use absorbent solution is solvent, prepares inner mark solution, wherein said absorbent solution to be volumetric concentration be 1% ammoniacal liquor-methanol solution;
(2) preparation of standard working solution: with pyridine, styrene and quinoline standard items for object, use absorbent solution is solvent, be prepared into Standard Stock solutions through stepwise dilution, then add a certain amount of inner mark solution respectively, be prepared into standard working solution;
(3) preparation of sample solution: gather the object in cigarette smoke, accurately adds the absorbent solution of a certain amount of inner mark solution and certain volume, mechanical shaking extraction, and scavenging solution obtains sample solution after crossing organic filter membrane;
(4) gas chromatography tandem mass spectrometry instrument is analyzed: carry out detection with gas chromatography tandem mass spectrometry instrument (GC-MS/MS) to standard working solution and sample solution and analyze;
(5) drafting of standard working curve and the calculating of sample result.
2. the method for half volatile material in mensuration cigarette mainstream flue gas according to claim 1, it is characterized in that, the preparation of described inner mark solution comprises the following steps:
(1) mark storing solution in: accurately take 0.1gD5-pyridine, 0.05gD8-styrene and 0.005gD7-quinoline, be accurate to 0.1mg, in the volumetric flask of 100mL, dissolve by absorbent solution and be settled to scale;
(2) inner mark solution: accurately pipette mark storing solution in 0.4mL, in the volumetric flask of 100mL, dilute by absorbent solution and be settled to scale.
3. the method for half volatile material in mensuration cigarette mainstream flue gas according to claim 1, it is characterized in that, the preparation of described standard working solution comprises the following steps:
(1) primary standard storing solution: accurately take 0.5g pyridine, 0.25g styrene and 0.025g quinoline, be accurate to 0.1mg, in the volumetric flask of 100mL, dissolves by absorbent solution and is settled to scale;
(2) secondary standard storing solution: accurately pipette 2mL primary standard storing solution, in the volumetric flask of 100mL, dilutes by absorbent solution and is settled to scale;
(3) standard working solution: accurately pipette secondary standard storing solution 10 μ L, 40 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L respectively, to in the volumetric flask of 10mL, accurately add 500 μ L inner mark solutions more respectively, be settled to scale with diluted absorption solution, obtain series standard working solution.
4. the method for half volatile material in mensuration cigarette mainstream flue gas according to claim 1, it is characterized in that, the preparation of described sample solution comprises the following steps:
(1) cigarette smoking: aspirate 20 cigarette according to the requirement of GB/T19609 standard, wherein with the granule phase substance in cambridge filter trapping cigarette mainstream flue gas, and be positioned over the gas gas-phase objects filled in the absorption bottle trapping cigarette mainstream flue gas of 20mL absorbent solution in ice cube/aqueous mixtures with 1;
(2) sample solution: the trapping that above step obtains had the cambridge filter of TPM to be positioned in 250mL conical flask, wherein filter disc answers full wafer to put into conical flask to pave, can not shred or tear up, and trapping has the absorbent solution of gas gas-phase objects to be all transferred in conical flask, and with 20mL absorbent solution washing absorption bottle several times, cleansing solution is transferred to conical flask in the lump, finally add 400 μ L inner mark solutions again, conical flask is placed in oscillator and extracts 30min under 160r/min condition, leave standstill a moment, get 2mL extract, use 0.45 μm of organic phase membrane filtration, obtain sample solution.
5. the method for half volatile material in mensuration cigarette mainstream flue gas according to claim 1, is characterized in that, described GC-MS/MS analyzes, and its instrumental conditions is: the DB-WAX capillary chromatographic column adopting 30m × 0.25mm × 0.25 μm specification; Carrier gas is helium, and constant current speed is 1.2mL/min; Input mode: sample size is 1 μ L, split sampling, and split ratio is 10:1; Injector temperature is 250 DEG C; Transmission line temperature is 280 DEG C; Heating schedule is initial temperature is 50 DEG C, is increased to 80 DEG C, then is increased to 240 DEG C with the speed of 10 DEG C/min with the speed of 2 DEG C/min, keeps 5min,
Its mass spectrophotometry condition is: ionization mode is EI source, positive ion mode; Ion source temperature: 230 DEG C; Quadrupole rod temperature: be 150 DEG C; Collision gas: nitrogen, flow velocity 1.5mL/min, carrier gas helium flow velocity is 2.25mL/min; Multiple-reaction monitoring MRM pattern, detail parameters is listed in the table below:
The MRM parameter list of object
。
6. the method for half volatile material in mensuration cigarette mainstream flue gas according to claim 1, it is characterized in that, described Specification Curve of Increasing and result are calculated as follows: with the ratio of the deuterated interior target concentration with it of object in standard working solution for horizontal ordinate, with the ratio of the deuterated interior target peak area with it of object in chromatogram for ordinate, carry out linear regression analysis, obtain standard working curve, by object in the sample solution that records under the same terms with it deuterated interior target chromatographic peak area ratio, substitute into standard working curve, the content of object in cigarette sample is tried to achieve according to following formula:
In formula:
W---the content of 3 kinds of half volatile materials in cigarette sample, unit is that microgram is often propped up, and μ g/ props up;
A---the peak area of 3 kinds of half volatile materials;
As---target peak area in corresponding;
The intercept of b---standard working curve;
Ms---target quality in adding, unit is microgram, μ g;
The slope of a---standard working curve;
The quantity of M---cigarette, unit is for propping up.
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