CN102353742A - 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 PDFInfo
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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
Technical field
The present invention relates to the method for a kind of static head space-gaschromatographic mass spectrometry selective determination cigarette, belong to the physical and chemical inspection technical field of cigarette with material with 7 kinds of benzene series things in the white glue with vinyl.
Background technology
Cigarette is an indispensable material in the production of cigarettes process with white glue with vinyl, and like glue for connecting, overlapping glue, packing glue etc. are because it tends to be brought into the objectionable constituent of benzene series things such as some benzene, toluene, ethylbenzene in production and process.The benzene series thing is the general designation that benzene, toluene, ethylbenzene, (adjacent,, to)-xylene, styrene etc. contain the mononuclear aromatics compound; Because this compounds all has acute or chronic, direct or indirect intoxicating effect to human body; What have can also be accumulated in the dna structure that organization internal changes cell; The serious harm health; Therefore the existence of this compounds not only has a strong impact on the sucking quality generation of cigarette, and directly has influence on the security of sucking of cigarette.In sum, cigarette there is important directive significance with the analysis monitoring of the benzene series thing in the white glue with vinyl to the sucking quality and the security of cigarette.
At present the detection traditional preprocessing means of benzene series thing mainly contain combination gas chromatography such as head space direct injected, purge and trap, head space liquid-phase extraction, headspace solid-phase microextraction and the gas chromatography combined with mass spectrometry technology is widely used at a plurality of analysis fields such as environment, medicine, food.The present invention considers cigarette white glue with vinyl particular physico-chemical characteristics, has selected static head space-gas chromatography-mass spectrum technology coupling selective determination cigarette with look benzene series thing in the white glue with vinyl.(static headspace SHS) is a kind of method that the head space gas that is in liquid or solid sample in the closed container that reaches balance is analyzed in static headspace analysis.It is directly got head space gas the volatile ingredient in the sample is analyzed; Can get rid of the interference of sample substrate effectively to analyzing; Need not the complicated sample preprocessing process; The mensuration process is easy, quick, thereby is used widely at a plurality of analysis fields such as food security, medicine analysis, industrial products in recent years.
Summary of the invention
The purpose of this invention is to provide the method for a kind of static head space-gaschromatographic mass spectrometry selective determination cigarette with 7 kinds of benzene series things in the white glue with vinyl.The present invention is directed to the deficiency of existing cigarette with benzene series thing residue analysis method in the white glue with vinyl; Static head space SHS is combined with gaschromatographic mass spectrometry (GC/MS), set up a kind of easy, accurate, fast selective and detect cigarette with the residual SHS-GC/MS method of benzene series thing in the white glue with vinyl.
Static head space of the present invention-gaschromatographic mass spectrometry selective determination cigarette is with the method for 7 kinds of benzene series things in the white glue with vinyl; With the methyl-n-butyl ketone is internal standard compound; Adopt static head space balance, gas chromatography-mass spectrum to select ion mode to measure the content of cigarette with 7 kinds of benzene series things in the white glue with vinyl; Wherein, Gas chromatography adopts the HP-INNOWAX chromatographic column, and assay adopts inner mark method ration.
Preferable, said cigarette use in the white glue with vinyl 7 kinds of benzene series things as benzene, toluene, ethylbenzene, ortho-xylene ,-xylene, right-xylene and styrene.
Said static head space-gaschromatographic mass spectrometry selective determination cigarette specifically comprises the steps: with the method for 7 kinds of benzene series things in the white glue with vinyl
(1) preparation of benzene series thing mixed standard solution: accurately take by weighing the pure material of 7 kinds of benzene series things, be made into mixed standard solution with glyceryl triacetate; It is subsequent use as stocking standard solution to be diluted to certain concentration;
(2) be added with in the preparation of target matrix correction agent: accurately take by weighing the internal standard compound methyl-n-butyl ketone, be made into the glyceryl triacetate solution of methyl-n-butyl ketone, target matrix correction agent in obtaining to be added with, and subsequent use as the matrix solvent with glyceryl triacetate;
Preferable, the preparation of target matrix correction agent can also adopt inner mark solution to prepare in said being added with.Being formulated as of said inner mark solution: accurately take by weighing the 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) drafting of the detection of benzene series thing mixed standard solution and typical curve: accurately the mixed standard solution of removing step (1) acquisition is many parts; Add the matrix solvent that a certain amount of step (2) obtains respectively; And obtain the mixed standard solution of a series of variable concentrations gradients with the glyceryl triacetate constant volume; After respectively the mixed standard solution of these a series of variable concentrations gradients being carried out static head space balance, put into head-space sampler respectively and carry out SHS-GC/MS and detect; Chromatographic peak area and interior mark peak area ratio Y with each benzene series thing are that ordinate, its respective quality concentration X (mg/L) are the typical curve that horizontal ordinate is drawn each benzene series thing, calculate the regression equation of each typical curve;
(4) the static head space of sample is handled: cigarette is placed the head space bottle with the white glue with vinyl sample, add institute's matrix prepared solvent, the testing sample solution of acquisition is sealed rapidly, carry out after the static head space balance to be measured;
(5) cigarette is with the assay of 7 kinds of benzene series things in the white glue with vinyl sample: the testing sample solution after the static head space balance is put into head-space sampler carry out SHS-GC/MS and detect; The ratio of the peak area of each benzene series thing of obtaining and the peak area of interior mark methyl-n-butyl ketone respectively in the corresponding regression equation of substitution, can be obtained the corresponding residual content of cigarette with 7 kinds of benzene series things in the white glue with vinyl sample.
Preferable, in the step (1), the concentration of every kind of benzene series thing is 10 μ g/mL-50 μ g/mL in the mixed standard solution.
Preferable, in the step (2), the concentration of methyl-n-butyl ketone is 1 μ g/mL-5 μ g/mL in the matrix solvent.
Preferable; In the step (3); The umber of the mixed standard solution that accurately pipettes is 6 parts, and in the mixed standard solution of a series of variable concentrations gradients that obtain, and the concentration of each benzene series thing 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.
Preferable, in step (3) neutralization procedure (4), the equilibrium temperature of static head space balance is 140 ℃, equilibration time is 20-40min; Be preferably 30min.
Preferable, in step (3) neutralization procedure (5), the static head space condition that SHS-GC/MS detects is:
Sample equilibrium temperature: 140 ℃; Sample loop temperature: 150 ℃; Transmission line temperature: 160 ℃; 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.
Preferable, in step (3) neutralization procedure (5), the GC/MS condition that SHS-GC/MS detects is:
GC conditions is: chromatographic column: HP-INNOWAX (60m * 0.25mm * 0.25 μ m); Injector temperature: 200 ℃; Carrier gas: high-purity helium, purity >=99.999%; The constant current mode of flow velocity: 1.0mL/min; Split ratio: 2: 1; Heating schedule: initial temperature keeps 3min for 40 ℃, and the speed with 2 ℃/min rises to 80 ℃ again, and the speed with 10 ℃/min rises to 180 ℃ then, keeps 15min;
The mass spectrum condition is: the transmission line temperature: 240 ℃; Ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Solvent delay: 8min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: select ion monitoring (SIM).
Preferable, in the step (4), every 0.25g cigarette generally adds the matrix solvent that 1-5ml is added with interior target with white glue with vinyl in the said testing sample solution.
The present invention with the special physicochemical property of white glue with vinyl, optionally measures cigarette with 7 kinds of benzene series things in the white glue with vinyl according to cigarette, has set up the content of static head space-gas chromatography-mass spectrum technology coupling selective determination cigarette with each benzene series thing in the white glue with vinyl.Sample is interior mark with methyl-n-butyl ketone behind the static head space of 140 ℃, 30min, adopts the HP-INNOWAX post, and gas chromatography-mass spectrum selects ion mode to detect inner mark method ration.This assay method is 0.008～0.01mg/kg to the detection by quantitative limit of 7 kinds of benzene series things; Recovery of standard addition is respectively 88.9～104.5%; Relative standard deviation is less than 5%.This assay method has characteristics such as simple quick, accurate sensitivity, is applied to the actual sample detection and has obtained good result.
Assay method of the present invention is directly got head space gas the volatile ingredient in the sample is analyzed; Can get rid of the interference of sample substrate effectively to analyzing; Need not the complicated sample preprocessing process; Avoided solvent-extracted loaded down with trivial details step; And through the SIM detection quantitatively, improved detection sensitivity greatly.Experimental result shows characteristics such as this assay method sample pre-treatments is easy and simple to handle, good reproducibility, accuracy height, rapid sensitive, is suitable for the mensuration of cigarette with residual benzene series thing in the white glue with vinyl.
Description of drawings
Fig. 1 head space equilibration time is to the figure that influences of peak area
Fig. 2 head space equilibrium temperature is to the figure that influences of peak area
Fig. 3 matrix correction agent blank is selected chromatography of ions figure
Wherein, a: glyceryl triacetate; B: dimethyl sulfoxide (DMSO); C:N, the N-dimethylformamide; D: normal hexane;
E: mark-on glyceryl triacetate
Wherein, 1: benzene; 2: toluene; 3: ethylbenzene; 4:2-hexanone (IS); 5: right-xylene; 6 :-xylene;
7: o-xylene; 8: styrene
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
1 experimental section
1.1 material, reagent and instrument
Cigarette is with white glue with vinyl sample (being selected from cigarette enterprise); Glyceryl triacetate (AR, chemical reagent Ltd of traditional Chinese medicines group); Normal hexane (chromatographically pure, Tianjin Da Mao chemical reagent factory); N, dinethylformamide (AR, chemical reagent factory of Chongqing Chuan Dong chemical industry (group) company limited); Dimethyl sulfoxide (DMSO) (AR, Tianjin chemistry chemical reagent company limited); Methyl-n-butyl ketone (interior mark, IS; 99%); Benzene (99%) (U.S. Sigma company); Toluene (99%) (U.S. Sigma company); Ethylbenzene (U.S. Sigma company); Adjacent,, right-xylene (U.S. Sigma company); Styrene (U.S. Sigma company); HP6890/5973 type gas chromatography appearance, 7694 automatic head space appearance (U.S. Agilent company); Analytical balance AG104 (sensibility reciprocal: 0.1mg, Switzerland Mettler Toledo Inc.)
1.2 sample preparation and analysis
Accurately take by weighing 7 kinds of each 0.1g of benzene series thing in the 50mL volumetric flask, use the glyceryl triacetate constant volume, the concentration that gets every kind of benzene series thing is 7 kinds of benzene series thing mixed standard solutions of 2mg/mL.Pipette 50 μ L and be settled to 10mL, the concentration of its each benzene series thing is 10 μ g/mL.
Accurately take by weighing 0.1g methyl-n-butyl ketone (IS) in the 25mL volumetric flask, use the glyceryl triacetate constant volume, get 4mg/mL IS solution.Get 40 μ L in the 100mL volumetric flask, use the glyceryl triacetate constant volume, subsequent use as the matrix solvent, its concentration is 1.6 μ g/mL.
Accurately take by weighing the 0.25g sample, place the head space bottle, add the glyceryl triacetate solution of 1mL 1.6 μ g/mL IS, compress bottle cap rapidly, put into head-space sampler and carry out the GC/MS check and analysis.The check and analysis condition is:
(1) SHS condition.Sample equilibrium temperature: 140 ℃; Sample loop temperature: 150 ℃; Transmission line temperature: 160 ℃; 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.Column: HP-INNOWAX (60m × 0.25mm × 0.25μm); inlet temperature: 200 ℃; carrier gas: helium purity, purity ≥ 99.999%; flow rate: 1.0mL/min (constant current mode); shunt ratio: 2:1; temperature program: temperature program:
Transfer line temperature: 240 ℃; ion source temperature 230 ℃; quadrupole temperature: 150 ℃; Solvent delay: 8min; ionization mode: EI source; ionization energy: 70eV; scanning : selected ion monitoring (SIM).
Retention time is compared in employing, the standard specimen addition method is qualitative, inner mark method ration under the SIM pattern.Retention time and the characteristic ion of 7 kinds of benzene series things and IS are seen table 1.
Retention time and the qualitative, quantitative ion of table 17 kind of benzene series thing and IS
2 results and discussion
2.1SHS the selection of equilibration time
SHS analyzes the influence that mainly is subjected to sample equilibrium temperature, equilibration time and sample substrate, therefore, adopts the mode of single factor experiment that these influence factors are selected.
With the concentration of every kind of benzene series thing is that 7 kinds of mixed standard solutions of 0.01 μ g/mL place the head space bottle, under identical equilibrium temperature to different equilibration times (5,10; 15,20,30; Head space gas 40min) is analyzed, and investigates the influence (see figure 1) of equilibration time to response.Visible by the result, under this equilibrium temperature, because the difference of the boiling point of each determinand, the optimum balance time is not quite similar.7 kinds of determinands all are that peak area response slightly increases through 5～30min basically, but change not quite, and peak area response slightly descends behind 30min, show that 30min equilibration time head space solution-air two reaches balance mutually basically.Take all factors into consideration, select 30min as equilibration time.
2.2SHS the selection of equilibrium temperature
Under identical equilibration time, descend the peak area response of 7 kinds of benzene series things in the static headspace gas to compare (see figure 2) to different equilibrium temperatures (80,90,100,120,140,150 ℃).The result shows that along with the raising of equilibrium temperature, the chromatographic peak area response increases gradually, and at 80～100 ℃, speedup is slower, and at 100～140 ℃, speedup is very fast, eases up subsequently.Take all factors into consideration the boiling point two aspect factors of cigarette with benzene series thing in self physicochemical property and to be measured 7 of white glue with vinyl, selecting 140 ℃ is equilibrium temperature.
2.3SHS the selection of matrix correction agent
Each components contents was both relevant with the volatility of itself in the head space gas, and was relevant with sample substrate again, the component of those solubleness in sample substrate big (partition factor is big) especially, and matrix effect is more obvious.Thereby make analytic sample and standard solution have identical matrix solvent, can eliminate the matrix effect of sample effectively, thereby improve the accuracy of quantitative test.Therefore, glyceryl triacetate, normal hexane, dimethyl sulfoxide and N are selected in this experiment respectively, and 4 kinds of organic solvents of dinethylformamide are investigated (see figure 3) as the matrix correction agent.The result shows; Normal hexane and the demonstration of dimethylsulfoxide solvent chromatogram are influenced by 78,91 characteristic ions; And N; The dinethylformamide solvent peak is influenced by 78,91,104,106 determinand characteristic ions; Thereby influence the accurately quantitative of sample, therefore be not suitable for the matrix correction agent of measuring as 7 kinds of benzene series things.The selection chromatography of ions figure of glyceryl triacetate is not subjected to the influence of determinand characteristic ion.In sum, selecting glyceryl triacetate for use is the matrix solvent.
2.4 chromatographic condition and interior target are selected
According to the structural property of determinand and consulting of pertinent literature, this The effects DB-624 (60m * 0.32mm * 1.8 μ m), 3 kinds of gas chromatographic columns of HP-VOC (60m * 0.32mm * 1.8 μ m) and HP-INNOWAX (60m * 0.25mm * 0.25 μ m) as analytical column 7 kinds of benzene series things of determinand are separated.The result shows; DB-624 (60m * 0.32mm * 1.8 μ m) and HP-VOC (60m * 0.32mm * 1.8 μ m) can not with right-xylene with-xylene separates fully; Select for use HP-INNOWAX (60m * 0.25mm * 0.25 μ m) chromatographic column then through to the optimization of initial temperature, temperature programme can with right-xylene with-xylene separates fully; All the other materials also can both obtain good baseline separation, thereby selection HP-INNOWAX (60m * 0.25mm * 0.25 μ m) is a stratographic analysis post (seeing Fig. 4 A-4C).When adopting head space-gas chromatography determination volatile compound, external standard method is adopted in quantitative test usually.Because it is bigger that the head space method is influenced by environment and sample substrate, makes the quantitative accuracy of external standard method receive certain limitation, internal standard method is attempted being used for head space-quantitative analysis by gas chromatography in recent years.This experiment selects for use methyl-n-butyl ketone to analyze as IS.The 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), so the selection methyl-n-butyl ketone is IS.
2.5 the detectability of working curve and method, the recovery, precision
The concentration that accurately pipettes each benzene series thing is 10 μ g/mL benzene series thing mixed standard solutions, 10,20,50,100,200,500 μ L in 6 10mL volumetric flasks; Adding 4 μ L concentration respectively is the IS solution of 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.Standard solution to these 6 grades of gradient concentrations carries out the SHS-GC/MS analysis respectively; And be that ordinate, its respective quality concentration X (mg/L) they are that horizontal ordinate carries out regretional analysis with each test substance chromatographic peak area and interior mark peak area ratio Y, regression equation and calculate detection limit respectively and detectability is seen 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
High 3 variable concentrations (0.05 during adding is hanged down respectively in the white glue with vinyl sample of known test substance (mean values of 6 mensuration); 0.1; 0.5 standard solution μ g/mL); Adopt the SHS-GC/MS method to measure the content of corresponding 7 kinds of determinands; According to measuring result and standard substance addition, the recovery of computing method (seeing table 3).The result shows that 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 the mensuration result is 0.7%～4.1%, less than 5%, shows that the repeatability of this method is better.
Table 3 cigarette is with the recovery and the precision (n=6) of benzene series thing in the white glue with vinyl glue
2.6 actual cigarette is with the mensuration of the benzene series thing residual quantity in the white glue with vinyl sample
Utilize said method that 7 kinds of cigarettes that cigarette enterprise uses are measured with the residual quantity of 7 kinds of benzene series things in the white glue with vinyl, all detect organism more than 4 kinds in each sample, see table 4 in detail.Wherein, with the interior target matrix correction agent of being added with of the corresponding 1ml of white glue with vinyl 0.25g, the concentration that is added with methyl-n-butyl ketone in the interior target matrix correction agent is 1.6 μ g/mL to 7 kinds of cigarettes being prepared with cigarette in the white glue with vinyl sample solution.
Table 4 cigarette is with the testing result (mg/kg) of benzene series thing in the white glue with vinyl
| The benzene | Sample | 1 | Sample 2 | |
Sample 4 | |
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 | |
| Right-xylene | 0.05 | 0.04 | 0.01 | 0.03 | 0.01 | 0.02 | 0.03 | |
| Between-xylene | 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 |
Annotate: ND: do not detect
3 conclusions
Set up the method for a kind of static head space-gas chromatography selective determination cigarette with 7 kinds of benzene series thing content in the white glue with vinyl, this method has been avoided solvent-extracted loaded down with trivial details step, and it is high quantitatively to have improved detection sensitivity greatly through the SIM detection.Experimental result shows characteristics such as this method sample pre-treatments is easy and simple to handle, good reproducibility, accuracy height, rapid sensitive, is suitable for the mensuration of cigarette with residual benzene series thing in the white glue with vinyl.
Claims (10)
1. static head space-gaschromatographic mass spectrometry selective determination cigarette is with the method for 7 kinds of benzene series things in the white glue with vinyl; It is characterized in that; With the methyl-n-butyl ketone is internal standard compound; Adopt static head space balance, gas chromatography-mass spectrum to select ion mode to measure the content of cigarette with 7 kinds of benzene series things in the white glue with vinyl; Wherein, Gas chromatography adopts the HP-INNOWAX chromatographic column, and assay adopts inner mark method ration.
2. static head space as claimed in claim 1-gaschromatographic mass spectrometry selective determination cigarette is with the method for 7 kinds of benzene series things in the white glue with vinyl; It is characterized in that, said cigarette use in the white glue with vinyl 7 kinds of benzene series things as benzene, toluene, ethylbenzene, ortho-xylene ,-xylene, right-xylene and styrene.
3. static head space as claimed in claim 1 or 2-gaschromatographic mass spectrometry selective determination cigarette is characterized in that with the method for 7 kinds of benzene series things in the white glue with vinyl, specifically comprises the steps:
(1) preparation of benzene series thing mixed standard solution: accurately take by weighing the pure material of 7 kinds of benzene series things, be made into mixed standard solution with glyceryl triacetate;
(2) be added with in the preparation of target matrix correction agent: accurately take by weighing the internal standard compound methyl-n-butyl ketone, be made into the glyceryl triacetate solution of methyl-n-butyl ketone, target matrix correction agent in obtaining to be added with, and subsequent use as the matrix solvent with glyceryl triacetate;
(3) drafting of the detection of benzene series thing mixed standard solution and typical curve: accurately the mixed standard solution of removing step (1) acquisition is many parts; Add the matrix solvent that a certain amount of step (2) obtains respectively; And obtain the mixed standard solution of a series of variable concentrations gradients with the glyceryl triacetate constant volume; After respectively the mixed standard solution of these a series of variable concentrations gradients being carried out static head space balance, put into head-space sampler respectively and carry out SHS-GC/MS and detect; Chromatographic peak area and interior mark peak area ratio Y with each benzene series thing are that ordinate, its respective quality concentration X (mg/L) are the typical curve that horizontal ordinate is drawn each benzene series thing, calculate the regression equation of each typical curve;
(4) the static head space of sample is handled: cigarette is placed the head space bottle with the white glue with vinyl sample, add institute's matrix prepared solvent, the testing sample solution of acquisition is sealed rapidly, carry out after the static head space balance to be measured;
(5) cigarette is with the assay of 7 kinds of benzene series things in the white glue with vinyl sample: the testing sample solution after the static head space balance is put into head-space sampler carry out SHS-GC/MS and detect; The ratio of the peak area of each benzene series thing of obtaining and the peak area of interior mark methyl-n-butyl ketone respectively in the corresponding regression equation of substitution, can be obtained the corresponding residual content of cigarette with 7 kinds of benzene series things in the white glue with vinyl sample.
4. static head space as claimed in claim 3-gaschromatographic mass spectrometry selective determination cigarette is characterized in that with the method for 7 kinds of benzene series things in the white glue with vinyl in the step (1), the concentration of every kind of benzene series thing is 10 μ g/mL-50 μ g/mL in the mixed standard solution.
5. static head space as claimed in claim 3-gaschromatographic mass spectrometry selective determination cigarette is characterized in that with the method for 7 kinds of benzene series things in the white glue with vinyl in the step (2), the concentration of methyl-n-butyl ketone is 1 μ g/mL-5 μ g/mL in the matrix solvent.
6. static head space as claimed in claim 3-gaschromatographic mass spectrometry selective determination cigarette is with the method for 7 kinds of benzene series things in the white glue with vinyl; It is characterized in that in the step (3), the umber of the mixed standard solution that accurately pipettes is 6 parts; And in the mixed standard solution of a series of variable concentrations gradients that obtain; The concentration of each benzene series thing 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.
7. static head space as claimed in claim 3-gaschromatographic mass spectrometry selective determination cigarette is with the method for 7 kinds of benzene series things in the white glue with vinyl; It is characterized in that; In step (3) neutralization procedure (4), the equilibrium temperature of static head space balance is 140 ℃, and equilibration time is 20-40min.
8. static head space as claimed in claim 3-gaschromatographic mass spectrometry selective determination cigarette is characterized in that with the method for 7 kinds of benzene series things in the white glue with vinyl in step (3) neutralization procedure (5), the static head space condition that SHS-GC/MS detects is:
Sample equilibrium temperature: 140 ℃; Sample loop temperature: 150 ℃; Transmission line temperature: 160 ℃; 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.
9. static head space as claimed in claim 3-gaschromatographic mass spectrometry selective determination cigarette is characterized in that with the method for 7 kinds of benzene series things in the white glue with vinyl 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 ℃; Carrier gas: high-purity helium, purity >=99.999%; The constant current mode of flow velocity: 1.0mL/min; Split ratio: 2: 1; Heating schedule: initial temperature keeps 3min for 40 ℃, and the speed with 2 ℃/min rises to 80 ℃ again, and the speed with 10 ℃/min rises to 180 ℃ then, keeps 15min;
Mass spectrum condition: transmission line temperature: 240 ℃; Ion source temperature: 230 ℃; Quadrupole rod temperature: 150 ℃; Solvent delay: 8min; Ionization mode: EI source; Ionizing energy: 70eV; Scan mode: SIM selects ion monitoring.
10. static head space as claimed in claim 3-gaschromatographic mass spectrometry selective determination cigarette is with the method for 7 kinds of benzene series things in the white glue with vinyl; It is characterized in that; In the step (4), every 0.25g cigarette adds the matrix solvent that 1-5ml is added with interior target with white glue with vinyl in the said testing sample solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102788861A (en) * | 2012-08-24 | 2012-11-21 | 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 |
| 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 |
| 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 |
| CN102879511A (en) * | 2012-09-27 | 2013-01-16 | 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 |
| CN103512994A (en) * | 2013-10-14 | 2014-01-15 | 福建中烟工业有限责任公司 | Method for measuring residual volatile components in cigarette filter stick |
| CN103512977A (en) * | 2013-09-24 | 2014-01-15 | 贵州中烟工业有限责任公司 | Method for selectively determining benzene series in smoke intercepted by cigarette filter through adopting static headspace-gas chromatography/mass spectrometry |
| 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 |
| CN104316636A (en) * | 2014-10-29 | 2015-01-28 | 广东中烟工业有限责任公司 | Method for internal standard determination of benzene and benzene series in glyceryl triacetate through headspace-gas mass spectrometry |
| CN105319283A (en) * | 2014-07-17 | 2016-02-10 | 上海市农药研究所 | Method for measuring content of terpyridine |
| CN105467030A (en) * | 2015-11-23 | 2016-04-06 | 内蒙古蒙牛乳业（集团）股份有限公司 | Method for detecting benzene series in dairy product |
| CN105823838A (en) * | 2016-03-15 | 2016-08-03 | 广东中烟工业有限责任公司 | Perfume component detection method taking glyceryl triacetate as solvent |
| CN105974008A (en) * | 2016-04-27 | 2016-09-28 | 广东中烟工业有限责任公司 | Method for detecting spice ingredient in flavoring glyceryl triacetate |
| CN105974011A (en) * | 2016-04-29 | 2016-09-28 | 浙江海洋学院 | Method for detecting leakage of PX |
| 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 |
| CN109856302A (en) * | 2018-01-17 | 2019-06-07 | 中国环境科学研究院 | A kind of gas-detecting device and its operating method for benzene homologues |
| CN111983087A (en) * | 2020-08-25 | 2020-11-24 | 甘肃烟草工业有限责任公司 | Method for measuring benzene, toluene, ethylbenzene, styrene and xylene in blasting beads or capsules |
| CN112630335A (en) * | 2020-12-16 | 2021-04-09 | 马钢奥瑟亚化工有限公司 | Method for determining contents of benzene, toluene and xylene in coal tar light oil fraction |
| CN117214334A (en) * | 2023-09-18 | 2023-12-12 | 中国科学院广州地球化学研究所 | Method for determining short-chain alkylbenzene series in hydrocarbon source rock |
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Cited By (27)
| 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 |
| CN102788861A (en) * | 2012-08-24 | 2012-11-21 | 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 |
| 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 |
| CN102879511A (en) * | 2012-09-27 | 2013-01-16 | 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 |
| 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 |
| CN103512977A (en) * | 2013-09-24 | 2014-01-15 | 贵州中烟工业有限责任公司 | Method for selectively determining benzene series in smoke intercepted by cigarette filter through adopting static headspace-gas chromatography/mass spectrometry |
| 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 |
| CN103512994A (en) * | 2013-10-14 | 2014-01-15 | 福建中烟工业有限责任公司 | Method for measuring residual volatile components in cigarette filter stick |
| 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 |
| CN104316636A (en) * | 2014-10-29 | 2015-01-28 | 广东中烟工业有限责任公司 | Method for internal standard determination of benzene and benzene series in glyceryl triacetate through headspace-gas mass spectrometry |
| CN105467030A (en) * | 2015-11-23 | 2016-04-06 | 内蒙古蒙牛乳业（集团）股份有限公司 | Method for detecting benzene series in dairy product |
| CN105823838A (en) * | 2016-03-15 | 2016-08-03 | 广东中烟工业有限责任公司 | Perfume component detection method taking glyceryl triacetate as solvent |
| CN105974008A (en) * | 2016-04-27 | 2016-09-28 | 广东中烟工业有限责任公司 | Method for detecting spice ingredient in flavoring glyceryl triacetate |
| CN105974011A (en) * | 2016-04-29 | 2016-09-28 | 浙江海洋学院 | Method for detecting leakage of PX |
| 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 |
| CN109856302A (en) * | 2018-01-17 | 2019-06-07 | 中国环境科学研究院 | A kind of gas-detecting device and its operating method for benzene homologues |
| 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 |
| CN111983087A (en) * | 2020-08-25 | 2020-11-24 | 甘肃烟草工业有限责任公司 | Method for measuring benzene, toluene, ethylbenzene, styrene and xylene in blasting beads or capsules |
| CN112630335A (en) * | 2020-12-16 | 2021-04-09 | 马钢奥瑟亚化工有限公司 | Method for determining contents of benzene, toluene and xylene in coal tar light oil fraction |
| CN117214334A (en) * | 2023-09-18 | 2023-12-12 | 中国科学院广州地球化学研究所 | Method for determining short-chain alkylbenzene series in hydrocarbon source rock |
| CN117214334B (en) * | 2023-09-18 | 2024-04-30 | 中国科学院广州地球化学研究所 | Method for determining short-chain alkylbenzene series in hydrocarbon source rock |
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