CN106596796A - Method for detecting 9 aromatic amines in mainstream smoke of cigarettes with GC-MS (gas chromatography-mass spectrometry) based on liquid-liquid micro-extraction - Google Patents
Method for detecting 9 aromatic amines in mainstream smoke of cigarettes with GC-MS (gas chromatography-mass spectrometry) based on liquid-liquid micro-extraction Download PDFInfo
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Abstract
The invention provides a method for detecting 9 aromatic amines in mainstream smoke of cigarettes with GC-MS (gas chromatography-mass spectrometry) based on liquid-liquid micro-extraction. The method is characterized in that aromatic amines released from mainstream smoke are captured by a Cambridge filter, an internal standard is added, the Cambridge filter obtained through suction is subjected to oscillating extraction with a hydrochloric acid water solution, pH is regulated to 12-13 by adding a sodium hydroxide water solution, a certain quantity of an extracting solvent toluene and a salting-out agent anhydrous sodium sulfate are added and shaken, an upper toluene layer is taken out after centrifugation, heptafluorobutyric anhydride is used for derivatization, dispersive solid-phase extraction purification is performed, then the content of aromatic amines in the obtained product is analyzed with GC-MS, and quantification is performed with an internal standard method. Sample pretreatment is simple and rapid to operate, analysis and detection time is short, and the method is good in repeatability and high in recovery rate and suitable for detecting the release content of the 9 aromatic amines in the mainstream smoke of the cigarettes.
Description
Technical field
The invention belongs to chemical analysis field, and in particular to a kind of to utilize liquid-liquid micro-extraction technology gas chromatography combined with mass spectrometry
Method（GC-MS）Quantitative analysis method to 9 kinds of aromatic amine burst sizes in cigarette mainstream flue gas.
Background technology
Aromatic amine is important organic synthesiss raw material and intermediate, be widely used in manufacture dyestuff, insecticide, medicine,
In the industrial process of rubber, aromatic polyurethane etc..Some aromatic amines, such as aniline, o- toluidines, 1- are there is also in cigarette smoke
Naphthylamines, 2- naphthylamines, 3- aminobphenyls, 4- aminobphenyls etc..International cancer research institution（IARC）By ortho-aminotoluene, 2- naphthylamines,
4- aminobphenyls are divided into I class carcinogens, and o-aminoanisole is divided into 2B class carcinogens.In view of the danger of aromatic amine material
Evil property, some aromatic amines are listed in cigarette mainstream flue gas also in the world needs in harmful smoke components list of the control with disclosure（Table
1）.Wherein it should be noted that food and drug administration（FDA）In issue in 2012 with regard to tobacco product and flue gas
In harmful substance and potentially harmful substance ingredient lists（HPHCs list）In except naphthalidine, 2- naphthylamines, 3- aminobphenyls,
Outside 4- aminobphenyls, o-aminoanisole, 2,6- dimethylanilines and ortho-aminotoluene are also additionally listed.
In the flue gas reported at present, the detection method of aromatic amine compounds mainly has gas chromatography（GC）, liquid phase color
Spectrum tandem mass spectrometry（LC-MSMS）, combined gas chromatography mass spectrometry（GC-MS）Deng.Wherein GC-MS methods are most widely used.
But as the content of aromatic amine in cigarette smoke is extremely low, generally ng/ is propped up, and complicated component in cigarette mainstream flue gas, therefore right
The detection of aromatic amine in cigarette mainstream flue gas generally comprises the complexity such as one or multi-step liquid-liquid extraction, Solid-Phase Extraction, concentration
Pretreatment process.Liquid-liquid micro-extraction is a kind of Sample Pretreatment Technique developed in recent years, and which can be considered that liquid-liquid extraction is molten
The processing procedure that agent is minimized.Currently, liquid-liquid micro-extraction technology because its have simplicity, extract thickening efficiency it is high the features such as, exist
In water phase, the analysis field of low pole material is extensively applied.Research is set up based on before liquid-liquid micro-extraction/dispersive solid-phase extraction purification
The analysis method of aromatic amine compounds is harmful in simple, effective, the accurate cigarette mainstream flue gas for processing, is objectively and accurately commented
The burst size of aromatic amine in valency cigarette product, for cigarette mainstream flue gas composition discloses significant with management and control.
The content of the invention
It is an object of the invention to provide 9 kinds of aromatic amines in a kind of cigarette mainstream flue gas（Naphthalidine, 2- naphthylamines, 3- amino connection
Benzene, 4- aminobphenyls, o-aminoanisole, 2,6- dimethylanilines, ortho-aminotoluene, meta-aminotoluene, para-totuidine）GC-MS
Analysis method, mainly carries out suction test to cigarette sample first, traps the aromatic amine in main flume with cambridge filter, so
Pretreatment is carried out using liquid-liquid micro-extraction pretreatment technology afterwards, is derived with heptafluorobutyric anhydride, it is purified rear using GC-MS pair
Aromatic amine is detected, and carries out quantitative analyses by internal standard method.
The purpose of the present invention is achieved through the following technical solutions：
In a kind of GC-MS detection cigarette mainstream flue gas based on liquid-liquid micro-extraction, the method for 9 kinds of aromatic amines, is filtered by Cambridge first
The aromatic amine of the release in piece trapping main flume, is added internal standard, the cambridge filter that suction is obtained is carried out with aqueous hydrochloric acid solution
Mechanical shaking extraction, adds sodium hydrate aqueous solution by pH regulator to 12 ~ 13, add a certain amount of extractant toluene, salting-out agents without
Aqueous sodium persulfate is shaked, and takes out upper toluene layer, performed the derivatization with heptafluorobutyric anhydride, be dispersed through Solid-Phase Extraction net after centrifugation
After change, fragrant amine content therein is analyzed with GC-MS, and is carried out quantitatively by internal standard method.Comprise the following steps that：
（1）Sample pre-treatments：
Method according to GB/T 5606. 1-2004 and GB/T 16447-2004 is sampled and adjusts 3R4F cigarette samples, trapping
Cigarette mainstream smoke condensate（10 cigarette mainstream smoke condensates are trapped under HCI suction modes, is trapped under ISO suction modes
20 cigarette mainstream smoke condensates）, the filter disc after trapping is positioned in 100 mL sample bottles, 60 mL 5% are separately added into
HCl/water solution and 50 L mixing internal standards, 45 min of oscillation extraction on the agitator, after whole extracting solution qualitative filter papers are filtered, use
4.0 mol/L NaOH solutions adjust pH to 12 ~ 13,2 mL toluene of addition and 2 g anhydrous sodium sulfates, liquid-liquid dispersions extraction of ocean eddies 2
Upper organic phase is taken out after min, 8000 r/min centrifugation, with 5 L heptafluorobutyric anhydrides（HFBA）Derivative 40 min, use anhydrous slufuric acid
Magnesium, N- propyl group ethylenediamines（PSA）As sample prepare liquid after purifying with C18 powder dispersive solid-phase extraction；
（2）Standard working solution is prepared：
Preparation includes preparation, 9 kinds of aromatic amines and 6 kinds of deuterated interior targets of 9 kinds of aromatic amines and 6 kinds of deuterated interior target list mark storing solutions
The preparation of mixed mark storing solution and the preparation of series standard working solution；
（3）GC-MS is determined：
The series standard working solution injection GC-MS that absorption is prepared, with comparing for standard series peak area and internal standard peak area
Its quality sets up equation of linear regression, and sample prepare liquid is measured, and measures the peak area and internal standard peak of each target aromatic amine
Area ratio, substitutes into equation of linear regression, respectively obtains the content of 9 kinds of aromatic amines in sample.
The detailed process that standard working solution is prepared is as follows：
Single mark storing solution：Using methanol as solvent prepare respectively mass concentration be 1 mg/mL 9 kinds of aromatic amines and 6 kinds it is deuterated
Interior target list mark storing solution；
Mixed mark storing solution：200 L ortho-aminotoluenes, meta-aminotoluene, para-totuidine are pipetted respectively；50 L naphthalidines, 2- naphthylamines；
20 L 2,6- dimethylanilines；10 L 3- aminobphenyls, 4- aminobphenyls, single mark storing solution of o-aminoanisole, with
Toluene is settled to 10 mL, obtains the mixing storing solution of 9 kinds of aromatic amines；The deuterated interior target list mark storages of 6 kinds of 50 L are pipetted respectively
Standby liquid, is settled to 25 mL with toluene, obtains 6 kinds of deuterated interior targets that mass concentration is 4 mg/mL and mixes storing solution；
Series standard working solution：0.01 mL, 0.02 mL, 0.05 mL, 0.1 mL, 0.2 mL, 0.3 mL are pipetted respectively accurately
9 kinds of aromatic amines mixing storing solution, be separately added into 6 kinds of 50L deuterated interior targets and mix storing solutions, be settled to dilution with toluene
2 mL, 5 L heptafluorobutyric anhydrides（HFBA）Derivative 40 min, with anhydrous magnesium sulfate, N- propyl group ethylenediamines（PSA）With C18 powder
Series standard working solution is obtained after dispersive solid-phase extraction purification.
GC-MS analysis conditions are as follows：
Chromatographic column：DB-35 elastic capillary-columns, 30 m × 0.25 mm × 0.25 m；Injector temperature：280℃；Ion
Source temperature：230℃；Transmission line temperature：280℃；Sample size：1µL；Splitless injecting samples；Carrier gas：Helium, constant current mode, flow
0.8 mL/min；Temperature programming：60 DEG C of 2 min of holding, then rise to 140 DEG C with the speed of 10 DEG C/min, then with 4 DEG C/min's
Speed rises to 190 DEG C, finally rises to 280 DEG C with the speed of 30 DEG C/min, keeps 20 min；
Mass Spectrometry Conditions：Transmission line temperature：280℃；Ionization mode：Electron bombardment ionization source（EI）；Ionizing energy：70 eV；Ion source temperature
Degree：260℃；Solvent delay：8 min；Using choice ion pattern（SIM）Scanning, detail parameters are as shown in table 2.
The present invention has the effect that：
（1）This method first passage liquid-liquid micro-extraction pre-treating method, establishes 9 kinds of aromatic amines in a kind of cigarette mainstream flue gas
Gaschromatographic mass spectrometry rapid assay methods.Mainly according to the characteristics of cigarette smoke sample, to liquid-liquid micro-extraction pre-treating method
Extraction solvent, salting-out agents etc. have carried out selection and optimization, and have investigated the impact of derivatization reagent consumption and cleanser.
（2）The sample pretreatment process of this method is simple, quick, greatlys save analysis time.
（3）The reproducible of this method, the response rate are high, it is adaptable to the inspection of 9 kinds of aromatic amine burst sizes in cigarette mainstream flue gas
Survey.
Description of the drawings：
Fig. 1：Assay method flow chart of the present invention.
Fig. 2：The chromatogram of standard working solution（Figure a is total ion current figure；Figure b is extraction ion figure）.
Specific embodiment
The present invention is described further with reference to example, but is not to limit the present invention.
Example 1：
（1）Instrument and reagent：
Thermo ISQ gas chromatograph-mass spectrometer（Thermo Fisher companies of the U.S.）；RM-200A rotating disc type smoking machines
（German Borgwaldt companies）；Labnet VX-200 vortex mixed instruments（Labnet companies of the U.S.）；High speed centrifuge（Germany
Sigma companies）；Milli-Q ultrapure water systems（Millipore companies of the U.S.）.
Ortho-aminotoluene（o-TOL）, meta-aminotoluene（m-TOL）, para-totuidine（p-TOL）, 2,6- dimethylanilines（2,6-
DMA）, o-aminoanisole（o-ASD）, naphthalidine（1-NA）, 2- naphthylamines（2-NA）, 3- aminobphenyls（3-ABP）, 4- amino connection
Benzene（4-ABP）, D9- ortho-aminotoluene（o-TOL-d9）、D7- o-aminoanisole（o-ASD-d7）、D7- naphthalidine（1-NA-d7）、
D7- 2- naphthylamines（2-NA-d7）、D11- 2,6- dimethylanilines（2,6-DMA-d11）、D9- 4- aminobphenyls（4-ABP-d9）（Moral
Dr. Ehrensorfer companies of state）；Toluene, normal hexane, t-butyl methyl ether（Chromatographically pure, J. T. Baker companies of the U.S.）, hydrogen
Sodium oxide, Sodium Chloride, sodium sulfate（Analysis is pure, Tianjin north Reagent Company）, 3 kinds of d-SPE purifications test kits respectively 150 mg
Anhydrous magnesium sulfate and 25 mg N- propyl group ethylenediamines（PSA）2 mL test kits（5021）；150 mg anhydrous magnesium sulfates, 50 mg
The 2 mL test kits of PSA（5022）；The 2 mL test kits of 150 mg anhydrous magnesium sulfates, 50 mg PSA and 50 mg C18（5122）
（Agilent companies of the U.S.）；3R4F reference cigarette samples.
The comparison of three kinds of test kits is preferably as follows：From the point of view of color by sample solution before and after purification, tri- kinds of purification reagents of Jing
After box process, the color of sample shoals, and GC-MS analysis results show, although for o-ToL, m-ToL and p-ToL,
Three kinds of cleansers response to which that signal has certain decrease, but not significantly, especially for 2,6-DMA, o-ASD, 1-NA, 2-
NA, 3-ABP, 4-ABP are substantially without impact.Therefore in view of the complexity of mainstream smoke constituents, final experimental selection containing 150 mg without
The purification test kit of water magnesium sulfate, 50 mg PSA and 50 mg C18 is purified to sample.
（2）Sample pre-treatments
Method according to GB/T 5606. 1-2004 and GB/T 16447-2004 is sampled and adjusts cigarette sample.HCI is aspirated
10 cigarette mainstream smoke condensates are trapped under pattern, 20 cigarette mainstream smoke condensates under ISO suction modes, are trapped.To catch
Filter disc after collection is positioned in 100 mL sample bottles, is separately added into 60 mL, 5% HCl/water solution and 50 L mixing internal standards, in
45 min of oscillation extraction on agitator, after whole extracting solution qualitative filter papers are filtered, with 4.0 mol/L NaOH solutions adjust pH to
12 ~ 13, add 2 mL Extraction solvents and 2 g salting-out agents, take out after 2 min of liquid-liquid dispersions extraction of ocean eddies, 8000 r/min centrifugation
Upper organic phase, uses heptafluorobutyric anhydride（HFBA）Derivative 40 min, with 150 mg anhydrous magnesium sulfates, 50 mg PSA and 50 mg
GC-MS analyses are carried out after the purification of C18 dispersive solid-phase extractions.
Wherein extractant, salting-out agents, derivatization reagent and Solid phase extraction composition is optimized.As a result
Show, during with toluene, t-butyl methyl ether, normal hexane as Extraction solvent, methylbenzene extraction efficiency preferably, therefore chooses toluene to extract
Agent.When Sodium Chloride and sodium sulfate is separately added into promote aromatic amine by water phase partitioning in toluene, the effect of sodium sulfate is more preferable,
Therefore it is salting-out agents to choose sodium sulfate.When the impact of derivatization reagent is investigated, PFPA and heptafluorobutyric anhydride difference are not
Greatly, but when with heptafluorobutyric anhydride as derivatization reagent, when 3-ABP and 4-ABP are detected capacity of resisting disturbance more preferably, therefore it is final with
Heptafluorobutyric anhydride is derivatization reagent, and its consumption is optimized, and as a result shows that 5 L heptafluorobutyric anhydrides are enough to ensure that derivative
Change complete.
（3）The preparation of standard working solution
The preparation of standard working solution mainly include the preparation of 9 kinds of aromatic amines and 6 kinds of deuterated interior target list mark storing solutions, 9 kinds it is fragrant
Fragrant amine and 6 kinds of deuterated interior targets mix the preparation of mark storing solution and the preparation of series standard working solution, and concrete process for preparation is such as
It is front described, it is not repeated herein.
（4）GC-MS analysis results
Series standard working solution is carried out into GC-MS analyses, its quality compared with standard series peak area and internal standard peak area
Set up equation of linear regression.Response rate experiment is carried out to 3R4F cigarette mainstream flue gas under ISO suction modes using mark-on method, is pressed
Signal to noise ratio S/N >=3 are calculated the detection limit of analysis method, the horizontal replication of low middle high three mark-ons 3 times.What method was evaluated
As a result（Such as table 3）Show, 9 kinds of aromatic amine linear relationships are good（R2>0.998）, the response rate of 3 mark-on levels 73.3% ~
Between 124.5%, relative standard deviation（RSD）For 0.2 ~ 9.6%, detection limit（LOD）For 0.03 ~ 0.08 ng/cig.
In the lower 3R4F cigarette mainstream flue gas of ISO and HCI patterns suction, 9 kinds of aromatic amine measurement results are shown in Table 4.
Additionally, the measurement result by the measurement result of the method with traditional existing national standard method is compared, as a result
As shown in table 5, it is seen that except the measurement result of 2,6-DMA has outside different, the method and tradition side for remaining 8 kinds of aromatic amine
The concordance of method measurement result is preferable.As the pretreatment process based on liquid-liquid micro-extraction of this method is simple, it is thus provided that
A kind of method of aromatic amine in fast and accurately main flume.
。
Claims (6)
1. a kind of method that GC-MS based on liquid-liquid micro-extraction detects 9 kinds of aromatic amines in cigarette mainstream flue gas, it is characterised in that：
Trap the aromatic amine of the release in main flume first by cambridge filter, add internal standard, suction is obtained with aqueous hydrochloric acid solution
Cambridge filter carry out mechanical shaking extraction, add sodium hydrate aqueous solution by pH regulator to 12 ~ 13, add a certain amount of extractant
Toluene, salting-out agents anhydrous sodium sulfate are shaked, and take out upper toluene layer, performed the derivatization with heptafluorobutyric anhydride, Jing after centrifugation
After dispersive solid-phase extraction purification, fragrant amine content therein is analyzed with GC-MS, and is carried out quantitatively by internal standard method.
2. method according to claim 1, it is characterised in that：9 kinds of aromatic amines are specially：Naphthalidine, 2- naphthylamines, 3- ammonia
Base biphenyl, 4- aminobphenyls, o-aminoanisole, 2,6- dimethylanilines, ortho-aminotoluene, meta-aminotoluene, para-totuidine.
3. method according to claim 1, it is characterised in that：Comprise the following steps that：
（1）Sample pre-treatments：
Method according to GB/T 5606. 1-2004 and GB/T 16447-2004 is sampled and adjusts 3R4F cigarette samples, trapping
Cigarette mainstream smoke condensate, the filter disc after trapping is positioned in 100 mL sample bottles, is separately added into 60 mL, 5% HCl/waters
Solution and 50 μ L mixing internal standards, 45 min of oscillation extraction on the agitator, after whole extracting solution qualitative filter papers are filtered, use 4.0
Mol/L NaOH solutions adjust pH to 12 ~ 13,2 mL toluene of addition and 2 g anhydrous sodium sulfates, liquid-liquid dispersions extraction of ocean eddies 2
Upper organic phase is taken out after min, 8000 r/min centrifugation, with 5 μ L heptafluorobutyric anhydrides（HFBA）Derivative 40 min, use anhydrous sulfur
Sour magnesium, N- propyl group ethylenediamines（PSA）As sample prepare liquid after purifying with C18 powder dispersive solid-phase extraction；
（2）Standard working solution is prepared：
Preparation includes preparation, 9 kinds of aromatic amines and 6 kinds of deuterated interior targets of 9 kinds of aromatic amines and 6 kinds of deuterated interior target list mark storing solutions
The preparation of mixed mark storing solution and the preparation of series standard working solution；
（3）GC-MS is determined：
The series standard working solution injection GC-MS that absorption is prepared, with comparing for standard series peak area and internal standard peak area
Its quality sets up equation of linear regression, and sample prepare liquid is measured, and measures the peak area and internal standard peak of each target aromatic amine
Area ratio, substitutes into equation of linear regression, respectively obtains the content of 9 kinds of aromatic amines in sample.
4. method according to claim 3, it is characterised in that：During trapping cigarette mainstream smoke condensate, HCI suction moulds
10 cigarette mainstream smoke condensates are trapped under formula, 20 cigarette mainstream smoke condensates under ISO suction modes, are trapped.
5. method according to claim 3, it is characterised in that：The detailed process that standard working solution is prepared is as follows：
Single mark storing solution：Using methanol as solvent prepare respectively mass concentration be 1 mg/mL 9 kinds of aromatic amines and 6 kinds it is deuterated
Interior target list mark storing solution；
Mixed mark storing solution：200 L ortho-aminotoluenes, meta-aminotoluene, para-totuidine are pipetted respectively；50 L naphthalidines, 2- naphthylamines；
20 L 2,6- dimethylanilines；10 L 3- aminobphenyls, 4- aminobphenyls, single mark storing solution of o-aminoanisole, with first
Benzene is settled to 10 mL, obtains the mixing storing solution of 9 kinds of aromatic amines；The deuterated interior target list mark deposits of 6 kinds of 50 L are pipetted respectively
Liquid, is settled to 25 mL with toluene, obtains 6 kinds of deuterated interior targets that mass concentration is 4 mg/mL and mixes storing solution；
Series standard working solution：0.01 mL, 0.02 mL, 0.05 mL, 0.1 mL, 0.2 mL, 0.3 mL are pipetted respectively accurately
9 kinds of aromatic amines mixing storing solution, be separately added into 6 kinds of 50 L deuterated interior targets and mix storing solutions, with dilution with toluene constant volume
To 2 mL, 5 L heptafluorobutyric anhydrides（HFBA）Derivative 40 min, with anhydrous magnesium sulfate, N- propyl group ethylenediamines（PSA）With C18 powder
Series standard working solution is obtained after dispersive solid-phase extraction purification.
6. method according to claim 3, it is characterised in that：GC-MS analysis conditions are as follows：
Chromatographic column：DB-35 elastic capillary-columns, 30 m × 0.25 mm × 0.25 m；Injector temperature：280℃；Ion
Source temperature：230℃；Transmission line temperature：280℃；Sample size：1 μL；Splitless injecting samples；Carrier gas：Helium, constant current mode, flow
0.8 mL/min；Temperature programming：60 DEG C of 2 min of holding, then rise to 140 DEG C with the speed of 10 DEG C/min, then with 4 DEG C/min's
Speed rises to 190 DEG C, finally rises to 280 DEG C with the speed of 30 DEG C/min, keeps 20 min；
Mass Spectrometry Conditions：Transmission line temperature：280℃；Ionization mode：Electron bombardment ionization source（EI）；Ionizing energy：70 eV；Ion source temperature
Degree：260℃；Solvent delay：8 min；Using choice ion pattern（SIM）Scanning.
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| CN106770783A (en) * | 2017-01-09 | 2017-05-31 | 国家烟草质量监督检验中心 | A kind of liquid-liquid micro-extraction closes 9 kinds of methods of aromatic amine in phase chromatographic tandem mass spectrography detection cigarette mainstream flue gas |
| CN108414661A (en) * | 2018-03-13 | 2018-08-17 | 中国医科大学 | Derivative gas chromatography-mass spectrometry method of ammonia content in a kind of detection biological sample |
| CN108982710A (en) * | 2018-09-28 | 2018-12-11 | 江苏德旺化工工业有限公司 | The detection method of polycyclic aromatic hydrocarbons (PAH) in a kind of dyestuff |
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