CN102353742B - Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum - Google Patents

Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum Download PDF

Info

Publication number
CN102353742B
CN102353742B CN201110293606.5A CN201110293606A CN102353742B CN 102353742 B CN102353742 B CN 102353742B CN 201110293606 A CN201110293606 A CN 201110293606A CN 102353742 B CN102353742 B CN 102353742B
Authority
CN
China
Prior art keywords
cigarette
sample
benzene
static headspace
benzene homologues
Prior art date
Application number
CN201110293606.5A
Other languages
Chinese (zh)
Other versions
CN102353742A (en
Inventor
刘剑
姬厚伟
聂长春
叶冲
万强
韩伟
王芳
Original Assignee
贵州中烟工业有限责任公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 贵州中烟工业有限责任公司 filed Critical 贵州中烟工业有限责任公司
Priority to CN201110293606.5A priority Critical patent/CN102353742B/en
Publication of CN102353742A publication Critical patent/CN102353742A/en
Application granted granted Critical
Publication of CN102353742B publication Critical patent/CN102353742B/en

Links

Abstract

The invention relates to a method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum, which belongs to the technical field of physical and chemical inspection of materials for the cigarette. In order to selectively measure the 7 benzene series in the white latex for the cigarette, a measuring method for selecting ion quantitation through the static headspace-gas chromatograph mass spectrum is established. A sample of the white latex for the cigarette is subjected to static headspace for 30min at the temperature of 140 DEG C, 2-hexanone is taken as an internal standard, an HP-INNOWAX column is adopted, the gas chromatograph-mass spectrum selects an ion mode to detect, and quantitaion is carried out through an internal standard method. The quantitative detection limit of the measuring method for the 7 benzene series is 0.008-0.01mg/kg; the recovery of standard addition is 88.9-104.5 percent, and the relative standard deviation is less than 5 percent. According to the measuring method, the complicated step of solvent extraction is avoided, the detection sensitivity is greatly improved through selecting ion detection and quantitation, the interference factor is less, the operation is simple, and the sensitivity and the repeatability are good.

Description

The method of 7 benzene series in white latex for Static Headspace-gaschromatographic mass spectrometry selective determination cigarette
Technical field
The method that the present invention relates to a kind of Static Headspace-gaschromatographic mass spectrometry selective determination cigarette 7 benzene series in white latex, belongs to the physical and chemical inspection technical field of rolling up smoking material.
Background technology
Cigarette white glue with vinyl is indispensable material in production of cigarettes process, as glue for connecting, overlapping glue, packaging glue etc., due to its produce and process in tend to be brought into the objectionable constituent of the benzene homologues such as some benzene, toluene, ethylbenzene.Benzene homologues is the general designation that benzene, toluene, ethylbenzene, (adjacent,, to)-dimethylbenzene, styrene etc. contain mononuclear aromatics compound, because this compounds all has acute or chronic, direct or indirect intoxicating effect to human body, the DNA structure that can also be accumulated in organization internal change cell having, serious harm health, therefore the existence of this compounds not only produces and has a strong impact on the sucking quality of cigarette, and directly has influence on the security of sucking of cigarette.In sum, to cigarette, with the analysis monitoring of the benzene homologues in white glue with vinyl, sucking quality and the security to cigarette has important directive significance.
The traditional pre-treatment means of detection of current benzene homologues mainly contain head space direct injected, purge and trap, head space liquid-phase extraction, headspace solid-phase microextraction etc. and are widely used at multiple analysis fields such as environment, medicine, food in conjunction with gas chromatography and gas phase hydrolysis and condensation.The present invention considers cigarette white glue with vinyl particular physico-chemical characteristics, has selected look benzene homologues in white glue with vinyl for Static Headspace-gas chromatography-mass spectrum technology coupling selective determination cigarette.It is a kind of method that the head space gas of liquid or solid sample in the closed container in reaching balance is analyzed that Static Headspace is analyzed (static headspace, SHS).It is directly got head space gas the volatile ingredient in sample is analyzed, can effectively get rid of sample substrate to the interference of analyzing, without complicated sample pretreatment process, mensuration process is easy, quick, thereby is used widely at multiple analysis fields such as food security, medicine analysis, industrial products in recent years.
Summary of the invention
The object of this invention is to provide the method for a kind of Static Headspace-gaschromatographic mass spectrometry selective determination cigarette 7 benzene series in white latex.The present invention is directed to the deficiency of existing cigarette with benzene homologues residue analysis method in white glue with vinyl, by Static Headspace SHS and gaschromatographic mass spectrometry (GC/MS) combination, set up a kind of easy, accurate, fast selective detection cigarette residual SHS-GC/MS method of benzene homologues in white glue with vinyl.
The method of 7 benzene series in white latex for Static Headspace-gaschromatographic mass spectrometry selective determination cigarette of the present invention, taking methyl-n-butyl ketone as internal standard compound, adopt Static Headspace balance, gas chromatography-mass spectrum choice ion pattern to measure the content of cigarette 7 benzene series in white latex, wherein, gas chromatography adopts HP-INNOWAX chromatographic column, and assay adopts inner mark method ration.
Preferably, described cigarette 7 benzene series in white latex is benzene, toluene, ethylbenzene, ortho-xylene, m-dimethylbenzene, p-dimethylbenzene and styrene.
The method of 7 benzene series in white latex for described Static Headspace-gaschromatographic mass spectrometry selective determination cigarette, specifically comprises the steps:
(1) preparation of benzene homologues mixed standard solution: accurately take the pure material of 7 kinds of benzene homologues, be made into mixed standard solution with glyceryl triacetate; Can also be diluted to certain concentration for subsequent use as stocking standard solution;
(2) be added with the preparation of interior target matrix correction agent: accurately take internal standard compound methyl-n-butyl ketone, be made into the glyceryl triacetate solution of methyl-n-butyl ketone with glyceryl triacetate, obtain and be added with interior target matrix correction agent, and for subsequent use as matrix solvent;
Preferably, described in be added with the preparation of interior target matrix correction agent, can also adopt inner mark solution to prepare.Being formulated as of described inner mark solution: accurately take internal standard compound methyl-n-butyl ketone, be made into the glyceryl triacetate solution of methyl-n-butyl ketone with glyceryl triacetate, as inner mark solution;
(3) detection of benzene homologues mixed standard solution and the drafting of typical curve: many parts of the mixed standard solutions that accurately removing step (1) obtains, the matrix solvent that adds respectively a certain amount of step (2) to obtain, and obtain the mixed standard solution of a series of variable concentrations gradients with glyceryl triacetate constant volume, respectively the mixed standard solution of these a series of variable concentrations gradients is carried out after Static Headspace balance, put into respectively head-space sampler and carry out SHS-GC/MS detection; Taking the chromatographic peak area of each benzene homologues and interior mark peak area ratio Y as ordinate, its respective quality concentration X (mg/L) draws the typical curve of each benzene homologues as horizontal ordinate, calculates the regression equation of each typical curve;
(4) the Static Headspace processing of sample: cigarette is placed in to head space bottle with white glue with vinyl sample, adds prepared matrix solvent, the testing sample solution of acquisition is sealed rapidly, carry out after Static Headspace balance to be measured;
(5) assay of 7 kinds of benzene homologues in white glue with vinyl sample for cigarette: the testing sample solution after Static Headspace balance is put into head-space sampler and carry out SHS-GC/MS detection, the peak area of the each benzene homologues obtaining and the ratio of the peak area of interior mark methyl-n-butyl ketone are distinguished in the corresponding regression equation of substitution, can be obtained the corresponding residual content of 7 kinds of benzene homologues in cigarette white glue with vinyl sample.
Preferably, in step (1), in mixed standard solution, the concentration of every kind of benzene homologues is 10 μ g/mL-50 μ g/mL.
Preferably, in step (2), in matrix solvent, the concentration of methyl-n-butyl ketone is 1 μ g/mL-5 μ g/mL.
Preferably, in step (3), the umber of the mixed standard solution accurately pipetting is 6 parts, and in the mixed standard solution of a series of variable concentrations gradients obtaining, and the concentration of each benzene homologues is respectively 0.01 μ g/mL in every part, 0.02 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL, 0.5 μ g/mL, the concentration of methyl-n-butyl ketone is 1.6 μ g/mL.
Preferably, in step (3) neutralization procedure (4), the equilibrium temperature of Static Headspace balance is 140 DEG C, and equilibration time is 20-40min; Be preferably 30min.
Preferably, in step (3) neutralization procedure (5), the Static Headspace condition that SHS-GC/MS detects is:
Sample equilibrium temperature: 140 DEG C; Sample loop temperature: 150 DEG C; Transmission line temperature: 160 DEG C; Sample equilibration time: 30min; Sample bottle moulding pressure: 15psi; Nebulizer gas pressure: 30psi; Pressing time: 0.20min; Inflationtime: 0.20min; Sample loop equilibration time: 0.05min; Sample injection time: 0.5min.
Preferably, in step (3) neutralization procedure (5), the GC/MS condition that SHS-GC/MS detects is:
GC conditions is: chromatographic column: (60m × 0.25mm × 0.25 μ m) for HP-INNOWAX; Injector temperature: 200 DEG C; Carrier gas: high-purity helium, purity >=99.999%; The constant current mode of flow velocity: 1.0mL/min; Split ratio: 2: 1; Heating schedule: 40 DEG C of maintenance 3min of initial temperature, then rise to 80 DEG C with the speed of 2 DEG C/min, and then rise to 180 DEG C with the speed of 10 DEG C/min, keep 15min;
Mass spectrum condition is: transmission line temperature: 240 DEG C; Ion source temperature: 230 DEG C; Quadrupole rod temperature: 150 DEG C; Solvent delay: 8min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: select ion monitoring (SIM).
Preferably, in step (4), in described testing sample solution, every 0.25g cigarette generally adds 1-5ml to be added with the matrix solvent of interior target by white glue with vinyl.
The present invention, according to the special physicochemical property of white glue with vinyl for cigarette, optionally measures cigarette 7 benzene series in white latex, has set up the content of Static Headspace-gas chromatography-mass spectrum technology coupling selective determination cigarette with each benzene homologues in white glue with vinyl.Sample, after 140 DEG C, 30min Static Headspace, taking methyl-n-butyl ketone as interior mark, adopts HP-INNOWAX post, and gas chromatography-mass spectrum choice ion pattern detects, inner mark method ration.This assay method is 0.008~0.01mg/kg to the quantitative detectability of 7 kinds of benzene homologues; Recovery of standard addition is respectively 88.9~104.5%; Relative standard deviation is less than 5%.The features such as it is simple and quick, accurate sensitive that this assay method has, are applied to actual sample detection and have obtained good result.
Assay method of the present invention is directly got head space gas the volatile ingredient in sample is analyzed, can effectively get rid of sample substrate to the interference of analyzing, without complicated sample pretreatment process, avoid solvent-extracted loaded down with trivial details step, and detect quantitatively by SIM, greatly improve detection sensitivity.Experimental result shows the features such as this assay method sample pre-treatments is easy and simple to handle, reproducible, accuracy is high, rapid sensitive, is suitable for the mensuration of cigarette with residual benzene homologues in white glue with vinyl.
Brief description of the drawings
The affect figure of Fig. 1 head space equilibration time on peak area
The affect figure of Fig. 2 head space equilibrium temperature on peak area
The blank sample of Fig. 3 matrix correction agent is selected chromatography of ions figure
Wherein, a: glyceryl triacetate; B: dimethyl sulfoxide (DMSO); C:N, N-dimethylformamide; D: normal hexane;
E: mark-on glyceryl triacetate
Total ion chromatogram 4A, 4B and the 4C of Fig. 4 standard model Scan, standard model SIM and sample Sample
Wherein, 1: benzene; 2: toluene; 3: ethylbenzene; 4:2-hexanone (IS); 5: p-dimethylbenzene; 6: m-dimethylbenzene;
7: o-xylene; 8: styrene
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Embodiment 1
1 experimental section
1.1 materials, reagent and instrument
White glue with vinyl sample for cigarette (being selected from cigarette enterprise); Glyceryl triacetate (AR, chemical reagent Ltd of traditional Chinese medicines group); Normal hexane (chromatographically pure, Tianjin great Mao chemical reagent factory); DMF (AR, Chongqing Chuan Dong chemical industry (group) company limited chemical reagent factory); Dimethyl sulfoxide (DMSO) (AR, Tianjin chemistry chemical reagent company limited); Methyl-n-butyl ketone (interior mark, IS; 99%); Benzene (99%) (Sigma company of the U.S.); Toluene (99%) (Sigma company of the U.S.); Ethylbenzene (Sigma company of the U.S.); Adjacent,, p-dimethylbenzene (Sigma company of the U.S.); Styrene (Sigma company of the U.S.); HP6890/5973 type Gc/ms Analyser, 7694 automatic head space instrument (Agilent company of the U.S.); Analytical balance AG104 (sensibility reciprocal: 0.1mg, Mettler Toledo Inc. of Switzerland)
1.2 sample preparation and analysis
Accurately take 7 kinds of each 0.1g of benzene homologues in 50mL volumetric flask, use glyceryl triacetate constant volume, 7 kinds of benzene homologues mixed standard solutions that the concentration that obtains every kind of benzene homologues is 2mg/mL.Pipette 50 μ L and be settled to 10mL, the concentration of its each benzene homologues is 10 μ g/mL.
Accurately take 0.1g methyl-n-butyl ketone (IS) in 25mL volumetric flask, use glyceryl triacetate constant volume, obtain 4mg/mL IS solution.Get 40 μ L in 100mL volumetric flask, use glyceryl triacetate constant volume, for subsequent use as matrix solvent, its concentration is 1.6 μ g/mL.
Accurately take 0.25g sample, be placed in head space bottle, add the glyceryl triacetate solution of 1mL 1.6 μ g/mL IS, compress rapidly bottle cap, put into head-space sampler and carry out GC/MS detection analysis.Detection analysis condition is:
(1) SHS condition.Sample equilibrium temperature: 140 DEG C; Sample loop temperature: 150 DEG C; Transmission line temperature: 160 DEG C; Sample equilibration time: 30min; Sample bottle moulding pressure: 15psi; Nebulizer gas pressure: 30psi; Pressing time: 0.20min; Inflationtime: 0.20min; Sample loop equilibration time: 0.05min; Sample injection time: 0.5min.
(2) GC/MS condition.(60m × 0.25mm × 0.25 μ m) for chromatographic column: HP-INNOWAX; Injector temperature: 200 DEG C; Carrier gas: high-purity helium, purity>=99.999%; Flow velocity: 1.0mL/min (constant current mode); Split ratio: 2: 1; Heating schedule: heating schedule: transmission line temperature: 240 DEG C; 230 DEG C of ion source temperatures; Quadrupole rod temperature: 150 DEG C; Solvent delay: 8min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: select ion monitoring (SIM).
Retention time is compared in employing, standard specimen addition method is qualitative, inner mark method ration under SIM pattern.The retention time of 7 kinds of benzene homologues and IS and characteristic ion are in table 1.
The retention time of table 17 kind of benzene homologues and IS and qualitative, quantitative ion
2 results and discussion
The selection of 2.1SHS equilibration time
SHS analyzes the impact that is mainly subject to sample equilibrium temperature, equilibration time and sample substrate, therefore, adopts the mode of single factor experiment to select these influence factors.
7 kinds of mixed standard solutions that are 0.01 μ g/mL by the concentration of every kind of benzene homologues are placed in head space bottle, under identical equilibrium temperature to different equilibration times (5,10,15,20,30,40min) head space gas analyze, investigate the impact (see Fig. 1) of equilibration time on response.From result, under this equilibrium temperature, due to the difference of the boiling point of each determinand, the optimum balance time is not quite similar.7 kinds of determinands are all that peak area response slightly increases through 5~30min substantially, but change not quite, and after 30min, peak area response slightly declines, and shows that 30min equilibration time head space solution-air two-phase reaches balance substantially.Consider, select 30min as equilibration time.
The selection of 2.2SHS equilibrium temperature
Under identical equilibration time, the peak area response of 7 kinds of benzene homologues in the lower static headspace gas of different equilibrium temperatures (80,90,100,120,140,150 DEG C) is compared to (seeing Fig. 2).Result shows, along with the raising of equilibrium temperature, chromatographic peak area response increases gradually, and at 80~100 DEG C, speedup is slower, and at 100~140 DEG C, speedup is very fast, eases up subsequently.The boiling point two aspect factors that consider benzene homologues in self physicochemical property and to be measured 7 of cigarette white glue with vinyl, selecting 140 DEG C is equilibrium temperature.
The selection of 2.3SHS matrix correction agent
In head space gas, the content of each component is both relevant with the volatility of itself, relevant with sample substrate again, the especially component of those solubleness large (partition factor is large) in sample substrate, and matrix effect is more obvious.Thereby make analytic sample and standard solution there is identical matrix solvent, can effectively eliminate the matrix effect of sample, thereby improve the accuracy of quantitative test.Therefore, this experiment selects respectively glyceryl triacetate, normal hexane, dimethyl sulfoxide and 4 kinds of organic solvents of DMF to investigate (seeing Fig. 3) as matrix correction agent.Result shows, normal hexane and the demonstration of dimethylsulfoxide solvent chromatogram are affected by 78,91 characteristic ions, and N, dinethylformamide solvent peak is affected by 78,91,104,106 determinand characteristic ions, thereby affect the accurate quantitative analysis of sample, be therefore not suitable as the matrix correction agent that 7 kinds of benzene homologues are measured.The selection chromatography of ions figure of glyceryl triacetate is not subject to the impact of determinand characteristic ion.In sum, selecting glyceryl triacetate is matrix solvent.
2.4 chromatographic conditions and interior target are selected
According to consulting of the structural property of determinand and pertinent literature, DB-624 has been investigated in this experiment, and (60m × 0.32mm × 1.8 μ m), (m) (60m × 0.25mm × 0.25 μ m) 3 kinds of gas chromatographic columns separates 7 kinds of benzene homologues of determinand as analytical column 60m × 0.32mm × 1.8 μ HP-VOC with HP-INNOWAX.Result shows, (m) (60m × 0.32mm × 1.8 μ m) can not separate p-dimethylbenzene with m-dimethylbenzene 60m × 0.32mm × 1.8 μ DB-624 completely with HP-VOC, (60m × 0.25mm × 0.25 μ m) chromatographic column passes through and p-dimethylbenzene can be separated completely with m-dimethylbenzene the optimization of initial temperature, temperature programme to select HP-INNOWAX, all the other materials also can obtain good baseline separation, thereby (60m × 0.25mm × 0.25 μ is m) stratographic analysis post (seeing Fig. 4 A-4C) to select HP-INNOWAX.In the time adopting Headspace-Gas Chromatography Analysis to measure volatile compound, quantitative test adopts external standard method conventionally.Due to head space method, affected by environment and sample substrate larger, makes the quantitative accuracy of external standard method be subject to certain limitation, and internal standard method is attempted for Headspace-Gas Chromatography Analysis quantitative test in recent years.This experiment selects methyl-n-butyl ketone to analyze as IS.Result shows: under same quality level condition, methyl-n-butyl ketone and 7 kinds of component mass spectrum responses to be measured are comparatively approaching, and with the degree of separation of component to be measured high (seeing Fig. 4 A-4C), therefore selection methyl-n-butyl ketone is IS.
The detectability of 2.5 working curves and method, the recovery, precision
The concentration that accurately pipettes each benzene homologues is 10 μ g/mL benzene homologues mixed standard solution 10,20,50,100,200,500 μ L in 6 10mL volumetric flasks, add respectively the IS solution that 4 μ L concentration are 4mg/mL, and be settled to 10mL with glyceryl triacetate, obtain concentration and be respectively 0.01,0.02,0.05,0.1,0.2,0.5 μ g/mL and IS concentration are 6 grades of gradient mixed standard solutions of 1.6 μ g/mL.Respectively the standard solution of these 6 grades of gradient concentrations is carried out to SHS-GC/MS analysis, and taking each test substance chromatographic peak area and interior mark peak area ratio Y as ordinate, its respective quality concentration X (mg/L) are as horizontal ordinate carries out regretional analysis, obtain regression equation and calculate respectively detection limit and detectability in table 2 with 3 times of signal to noise ratio (S/N ratio)s (S/N=3) and 10 times of signal to noise ratio (S/N ratio)s.
Table 2 working curve and detectability
In the white glue with vinyl sample of known test substance (mean value of measuring for 6 times), add respectively low middle high 3 variable concentrations (0.05,0.1,0.5 μ g/mL) standard solution, adopt SHS-GC/MS method to measure the content of corresponding 7 kinds of determinands, according to measurement result and standard substance addition, the recovery (in table 3) of computing method.Result demonstration, the recovery of determinand is 88.9%~104.5%, shows that the accuracy of this method is higher; Calculating determinand relative standard deviation (RSD) according to measurement result is 0.7%~4.1%, is less than 5%, shows that the repeatability of this method is better.
The recovery and the precision (n=6) of benzene homologues in white glue with vinyl glue for table 3 cigarette
The mensuration of the residual benzene homologues in white glue with vinyl sample for 2.6 actual cigarettes
Utilize the residual quantity of the 7 kind cigarette 7 benzene series in white latexes of said method to cigarette enterprise use to measure, in each sample, all detect more than 4 kinds organism, in detail in table 4.Wherein, in 7 kinds of cigarette white glue with vinyl sample solutions preparing the corresponding 1ml of cigarette white glue with vinyl 0.25g be added with interior target matrix correction agent, the concentration that is added with methyl-n-butyl ketone in interior target matrix correction agent is 1.6 μ g/mL.
The testing result (mg/kg) of benzene homologues in white glue with vinyl for table 4 cigarette
Benzene homologues Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7
Benzene ??0.37 ??0.06 ??0.39 ??0.10 ??0.50 ??0.27 ??ND
Toluene ??0.04 ??0.23 ??0.08 ??0.06 ??0.03 ??0.05 ??0.03
Ethylbenzene ??0.04 ??0.07 ??0.03 ??0.04 ??0.02 ??0.03 ??0.05
P-dimethylbenzene ??0.05 ??0.04 ??0.01 ??0.03 ??0.01 ??0.02 ??0.03
M-dimethylbenzene ??0.10 ??0.06 ??ND ??0.03 ??0.01 ??0.02 ??0.07
Ortho-xylene ??0.10 ??0.05 ??ND ??0.03 ??ND ??ND ??0.04
Styrene ??ND ??0.03 ??ND ??0.02 ??ND ??0.01 ??ND
Note: ND: do not detect
3 conclusions
The method of having set up a kind of Static Headspace-gas chromatography/mass spectrometry selective determination cigarette 7 benzene series in white latex content, the method has been avoided solvent-extracted loaded down with trivial details step, and detects by SIM that quantitatively greatly to have improved detection sensitivity high.Experimental result shows the features such as the method sample pre-treatments is easy and simple to handle, reproducible, accuracy is high, rapid sensitive, is suitable for the mensuration of cigarette with residual benzene homologues in white glue with vinyl.

Claims (5)

1. a method for 7 benzene series in white latex for Static Headspace-gaschromatographic mass spectrometry selective determination cigarette, is characterized in that, specifically comprises the steps:
(1) preparation of benzene homologues mixed standard solution: accurately take the pure material of 7 kinds of benzene homologues, be made into mixed standard solution with glyceryl triacetate;
(2) be added with the preparation of interior target matrix correction agent: accurately take internal standard compound 2 – hexanones, be made into the glyceryl triacetate solution of 2 – hexanones with glyceryl triacetate, obtain and be added with interior target matrix correction agent, and for subsequent use as matrix solvent;
(3) detection of benzene homologues mixed standard solution and the drafting of typical curve: many parts of the mixed standard solutions that accurately removing step (1) obtains, the matrix solvent that adds respectively a certain amount of step (2) to obtain, and obtain the mixed standard solution of a series of variable concentrations gradients with glyceryl triacetate constant volume, respectively the mixed standard solution of these a series of variable concentrations gradients is carried out after Static Headspace balance, put into respectively head-space sampler and carry out SHS-GC/MS detection; Taking the chromatographic peak area of each benzene homologues and interior mark peak area ratio Y as ordinate, its respective quality concentration X mg/L draws the typical curve of each benzene homologues as horizontal ordinate, calculates the regression equation of each typical curve;
(4) the Static Headspace processing of sample: cigarette is placed in to head space bottle with white glue with vinyl sample, adds prepared matrix solvent, the testing sample solution of acquisition is sealed rapidly, carry out after Static Headspace balance to be measured;
(5) assay of 7 kinds of benzene homologues in white glue with vinyl sample for cigarette: the testing sample solution after Static Headspace balance is put into head-space sampler and carry out SHS-GC/MS detection, the peak area of the each benzene homologues obtaining and the ratio of the peak area of interior mark 2 – hexanones are distinguished in the corresponding regression equation of substitution, can be obtained the corresponding residual content of 7 kinds of benzene homologues in cigarette white glue with vinyl sample;
Described cigarette 7 benzene series in white latex is benzene, toluene, ethylbenzene, ortho-xylene, m-dimethylbenzene, p-dimethylbenzene and styrene;
In step (3) neutralization procedure (4), the equilibrium temperature of Static Headspace balance is 140 DEG C, and equilibration time is 20-40min;
In step (3) neutralization procedure (5), the Static Headspace condition that SHS-GC/MS detects is:
Sample equilibrium temperature: 140 DEG C; Sample loop temperature: 150 DEG C; Transmission line temperature: 160 DEG C; Sample equilibration time: 30min; Sample bottle moulding pressure: 15psi; Nebulizer gas pressure: 30psi; Pressing time: 0.20min; Inflationtime: 0.20min; Sample loop equilibration time: 0.05min; Sample injection time: 0.5min
In step (3) neutralization procedure (5), the GC/MS condition that SHS-GC/MS detects is:
GC conditions: chromatographic column: HP-INNOWAX; Injector temperature: 200 DEG C; Carrier gas: high-purity helium, purity >=99.999%; The constant current mode of flow velocity: 1.0mL/min; Split ratio: 2:1; Heating schedule: 40 DEG C of maintenance 3min of initial temperature, then rise to 80 DEG C with the speed of 2 ° of C/min, and then rise to 180 DEG C with the speed of 10 ° of C/min, keep 15min;
Mass spectrum condition: transmission line temperature: 240 DEG C; Ion source temperature: 230 DEG C; Quadrupole rod temperature: 150 DEG C; Solvent delay: 8min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: SIM selects ion monitoring.
2. the method for 7 benzene series in white latex for Static Headspace-gaschromatographic mass spectrometry selective determination cigarette as claimed in claim 1, is characterized in that, in step (1), in mixed standard solution, the concentration of every kind of benzene homologues is 10 μ g/mL-50 μ g/mL.
3. the method for 7 benzene series in white latex for Static Headspace-gaschromatographic mass spectrometry selective determination cigarette as claimed in claim 1, is characterized in that, in step (2), in matrix solvent, the concentration of 2 – hexanones is 1 μ g/mL-5 μ g/mL.
4. the method for 7 benzene series in white latex for Static Headspace-gaschromatographic mass spectrometry selective determination cigarette as claimed in claim 1, it is characterized in that, in step (3), the umber of the mixed standard solution accurately pipetting is 6 parts, and in the mixed standard solution of a series of variable concentrations gradients that obtain, in every part, the concentration of each benzene homologues is respectively 0.01 μ g/mL, 0.02 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL, 0.5 μ g/mL, the concentration of 2 – hexanones is 1.6 μ g/mL.
5. the method for 7 benzene series in white latex for Static Headspace-gaschromatographic mass spectrometry selective determination cigarette as claimed in claim 1, it is characterized in that, in step (4), in described testing sample solution, every 0.25g cigarette adds 1-5ml to be added with interior target matrix solvent by white glue with vinyl.
CN201110293606.5A 2011-09-29 2011-09-29 Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum CN102353742B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110293606.5A CN102353742B (en) 2011-09-29 2011-09-29 Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110293606.5A CN102353742B (en) 2011-09-29 2011-09-29 Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum

Publications (2)

Publication Number Publication Date
CN102353742A CN102353742A (en) 2012-02-15
CN102353742B true CN102353742B (en) 2014-06-25

Family

ID=45577346

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110293606.5A CN102353742B (en) 2011-09-29 2011-09-29 Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum

Country Status (1)

Country Link
CN (1) CN102353742B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102830194A (en) * 2012-07-06 2012-12-19 复旦大学 Method for rapidly detecting residual amount of benzene-based pollutants in plastic particles
CN102788861B (en) * 2012-08-24 2014-04-16 浙江省海洋水产研究所 Method for catching and detecting static headspace gas chromatography electrons of eleven chlorobenzene compounds in water
CN102854279A (en) * 2012-09-14 2013-01-02 江苏中烟工业有限责任公司 Method for determining contents of benzene and benzene-series substances in tobacco-use triacetin
CN102866223A (en) * 2012-09-14 2013-01-09 浙江出入境检验检疫局检验检疫技术中心 Method for determining benzene and methylbenzene residue in nail polish by utilizing headspace-gas-chromatography mass spectrometry
CN102879511B (en) * 2012-09-27 2014-10-15 甘肃烟草工业有限责任公司 Method for determining volatile organic compounds in polyvinyl acetate type water-based adhesive
CN103512977B (en) * 2013-09-24 2015-09-02 贵州中烟工业有限责任公司 The method of benzene homologues in Static Headspace-gaschromatographic mass spectrometry selective determination cigarette filter tip entrapping flue gas
CN103512994B (en) * 2013-10-14 2015-11-18 福建中烟工业有限责任公司 A kind ofly measure the residual method of volatile ingredient in filter stick for cigarettes
CN105319283A (en) * 2014-07-17 2016-02-10 上海市农药研究所 Method for measuring content of terpyridine
CN104165958A (en) * 2014-08-20 2014-11-26 云南中烟工业有限责任公司 Method for measuring content of benzene and benzene series in glycerol triacetate
CN104316636B (en) * 2014-10-29 2016-11-23 广东中烟工业有限责任公司 Utilize the internal standard assay method of benzene and benzene homologues in the glyceryl triacetate of head space-gaseous mass spectrum
CN105467030B (en) * 2015-11-23 2018-07-13 内蒙古蒙牛乳业(集团)股份有限公司 The method for detecting benzene homologues in dairy products
CN105823838B (en) * 2016-03-15 2019-05-07 广东中烟工业有限责任公司 It is a kind of using glyceryl triacetate as the component detection method of the fragrance of solvent
CN105974008B (en) * 2016-04-27 2019-05-07 广东中烟工业有限责任公司 The detection method of fragrance component in a kind of flavoring glyceryl triacetate
CN105974011B (en) * 2016-04-29 2018-10-12 浙江海洋学院 Method about detection PX leakages
CN106596826A (en) * 2017-01-25 2017-04-26 江苏中烟工业有限责任公司 Method for determining benzene and benzene series content in cellulose acetate fiber and cellulose acetate fiber mouth stick
CN108181417A (en) * 2017-12-15 2018-06-19 舟山出入境检验检疫局综合技术服务中心 A kind of method of dimethylbenzene in HS-GC-MS/MS detections marine product
CN109856302B (en) * 2018-01-17 2020-12-25 中国环境科学研究院 Gas detection device for benzene series and operation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
徐昕荣 等.顶空-气质联用法测定烟用粘合剂中苯系物.《广东化工》.2010,第37卷(第208期),摘要,第1.1节至第2.7节.
李国智 等.烟用水基型乳胶中苯系物的GC/MS/SIM测定.《烟草科技》.2009,(第10期),摘要. *
顶空-气质联用法测定烟用粘合剂中苯系物;徐昕荣 等;《广东化工》;20101231;第37卷(第208期);摘要,第1.1节至第2.7节 *

Also Published As

Publication number Publication date
CN102353742A (en) 2012-02-15

Similar Documents

Publication Publication Date Title
Stashenko et al. Sampling volatile compounds from natural products with headspace/solid-phase micro-extraction
Abdel-Rehim New trend in sample preparation: on-line microextraction in packed syringe for liquid and gas chromatography applications: I. Determination of local anaesthetics in human plasma samples using gas chromatography–mass spectrometry
Zheng et al. Evaluating polymer monolith in-tube solid-phase microextraction coupled to liquid chromatography/quadrupole time-of-flight mass spectrometry for reliable quantification and confirmation of quinolone antibacterials in edible animal food
El-Beqqali et al. Fast and sensitive environmental analysis utilizing microextraction in packed syringe online with gas chromatography–mass spectrometry: Determination of polycyclic aromatic hydrocarbons in water
CN104316634B (en) The measuring method of volatile organic acids in a kind of cigarette mainstream flue gas
CN102735784B (en) Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum
Hassan et al. Rapid and simple low density miniaturized homogeneous liquid–liquid extraction and gas chromatography/mass spectrometric determination of pesticide residues in sediment
Rodziewicz et al. Rapid determination of chloramphenicol residues in milk powder by liquid chromatography–elektrospray ionization tandem mass spectrometry
Wang et al. Ultrasonication extraction and gel permeation chromatography clean-up for the determination of polycyclic aromatic hydrocarbons in edible oil by an isotope dilution gas chromatography–mass spectrometry
CN104678039B (en) Measure the method for four kinds of aflatoxin contents in tobacco and tobacco product based on Liquid Chromatography-tandem Mass simultaneously
Wang et al. Multiresidue determination of fluoroquinolones, organophosphorus and N-methyl carbamates simultaneously in porcine tissue using MSPD and HPLC–DAD
CN103913528B (en) Quantitative detection method for pyrethriods pesticides in fresh tea
Risticevic et al. Protocol for the development of automated high-throughput SPME–GC methods for the analysis of volatile and semivolatile constituents in wine samples
Sannino et al. GC/CI–MS/MS method for the identification and quantification of volatile N-nitrosamines in meat products
Shah et al. Headspace analyses of acetone: a rapid method for measuring the 2H-labeling of water
Camarasu et al. Recent progress in the determination of volatile impurities in pharmaceuticals
CN102854271B (en) Method for measuring residues of three phenoxy carboxylic acid pesticides in tobacco and tobacco products
Chen et al. Dynamic ultrasound-assisted extraction coupled on-line with solid support derivatization and high-performance liquid chromatography for the determination of formaldehyde in textiles
Li et al. Gas chromatography–mass spectrometric analysis of hexanal and heptanal in human blood by headspace single-drop microextraction with droplet derivatization
CN105866302B (en) A kind of method that 7 kinds of biogenic amines in phase chromatogram concatenation QDa while quick detection white wine are closed using ultra high efficiency
CN102879519B (en) One ion chromatographic separation-electric conductivity detector detects chromic method in cigarette paper
Midey et al. High-performance ion mobility spectrometry with direct electrospray ionization (ESI-HPIMS) for the detection of additives and contaminants in food
CN107192788B (en) The gas chromatography-mass spectrum screening method of unknown poisonous substance in blood
Lovestead et al. Detection of poultry spoilage markers from headspace analysis with cryoadsorption on a short alumina PLOT column
CN107037149B (en) Fipronil and its metabolite residue amount method for measuring in a kind of egg

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant