CN106596796B - The method that GC-MS based on liquid-liquid micro-extraction surveys aromatic amine in cigarette smoke - Google Patents
The method that GC-MS based on liquid-liquid micro-extraction surveys aromatic amine in cigarette smoke Download PDFInfo
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Abstract
A method of 9 kinds of aromatic amines in the GC-MS detection cigarette mainstream flue gas based on liquid-liquid micro-extraction, it is characterized by: the aromatic amine of the release in main flume is trapped by cambridge filter first, internal standard is added, mechanical shaking extraction is carried out to the cambridge filter that suction obtains with aqueous hydrochloric acid solution, sodium hydrate aqueous solution is added, pH is adjusted to 12 ~ 13, a certain amount of extractant toluene is added, salting-out agents anhydrous sodium sulfate is shaked, upper toluene layer is taken out after centrifugation, it is performed the derivatization with heptafluorobutyric anhydride, after being dispersed Solid phase extraction, fragrant amine content therein is analyzed with GC-MS, and it is quantified by internal standard method.The sample pre-treatments of this method are easy to operate, quick, and the analysis detection time is short, and the reproducible of method, the rate of recovery are high, the detection of 9 kinds of aromatic amine burst sizes suitable for cigarette mainstream flue gas.
Description
Technical field
The invention belongs to chemical analysis fields, and in particular to a kind of to utilize liquid-liquid micro-extraction technology gas chromatography combined with mass spectrometry
Quantitative analysis method of the method (GC-MS) to 9 kinds of aromatic amine burst sizes in cigarette mainstream flue gas.
Background technique
Aromatic amine is important organic synthesis raw material and intermediate, be widely used in manufacture dyestuff, insecticide, drug,
In the industrial process of rubber, aromatic polyurethane etc..There is also some aromatic amines in cigarette smoke, such as aniline, o- toluidines, 1-
Naphthylamines, 2- naphthylamines, 3- aminobphenyl, 4- aminobphenyl etc..International cancer research institution (IARC) by ortho-aminotoluene, 2- naphthylamines,
4- aminobphenyl is divided into I class carcinogenic substance, and o-aminoanisole is divided into 2B class carcinogenic substance.In view of the danger of aromatic amine substance
Evil property, some aromatic amines, which are also listed in cigarette mainstream flue gas, in the world needs (table in the harmful smoke components list of control and disclosure
1).Wherein it is worth noting that, food and drug administration (FDA) in 2012 publication about tobacco product and flue gas
In harmful substance and potentially harmful substance ingredient lists (HPHCs list) in addition to naphthalidine, 2- naphthylamines, 3- aminobphenyl,
Except 4- aminobphenyl, o-aminoanisole, 2,6- dimethylaniline and ortho-aminotoluene are also additionally listed.
The detection method of aromatic amine compounds mainly has gas chromatography (GC), liquid phase color in the flue gas reported at present
Compose tandem mass spectrometry (LC-MSMS), combined gas chromatography mass spectrometry (GC-MS) etc..Wherein GC-MS method is most widely used.
But since the content of aromatic amine in cigarette smoke is extremely low, generally ng/ branch, and complicated component in cigarette mainstream flue gas, therefore it is right
The detection of aromatic amine generally comprises the complexity such as one or more steps liquid-liquid extraction, Solid Phase Extraction, concentration in cigarette mainstream flue gas
Pretreatment process.Liquid-liquid micro-extraction is a kind of Sample Pretreatment Technique developed in recent years, can be considered that liquid-liquid extraction is molten
The treatment process that agent minimizes.Currently, liquid-liquid micro-extraction technology exists because it has the characteristics that easy, to extract thickening efficiency high
The analysis field of low pole substance is widely applied in water phase.Research is established based on before liquid-liquid micro-extraction/dispersive solid-phase extraction purification
The analysis method of harmful aromatic amine compounds, is objectively and accurately commented in simple, effective, the accurate cigarette mainstream flue gas of processing
The burst size of aromatic amine in valence cigarette product discloses cigarette mainstream flue gas ingredient and is of great significance with control.
Summary of the invention
The object of the present invention is to provide 9 kinds of aromatic amines (naphthalidine, 2- naphthylamines, 3- amino connection in a kind of cigarette mainstream flue gas
Benzene, 4- aminobphenyl, o-aminoanisole, 2,6- dimethylaniline, ortho-aminotoluene, meta-aminotoluene, para-totuidine) GC-MS
Analysis method mainly carries out suction test to cigarette sample first, with the aromatic amine in cambridge filter trapping main flume, so
It is pre-processed using liquid-liquid micro-extraction pretreatment technology, is derived with heptafluorobutyric anhydride afterwards, use GC-MS pairs after purified
Aromatic amine is detected, and carries out quantitative analysis by internal standard method.
The purpose of the present invention is achieved through the following technical solutions:
A method of 9 kinds of aromatic amines in the GC-MS detection cigarette mainstream flue gas based on liquid-liquid micro-extraction pass through sword first
Bridge filter disc traps the aromatic amine of the release in main flume, and internal standard is added, the cambridge filter obtained with aqueous hydrochloric acid solution to suction
Mechanical shaking extraction is carried out, sodium hydrate aqueous solution is added by pH and is adjusted to 12 ~ 13, a certain amount of extractant toluene is added, saltouts
Agent anhydrous sodium sulfate is shaked, and upper toluene layer is taken out after centrifugation, is performed the derivatization with heptafluorobutyric anhydride, is dispersed solid phase extraction
After taking purification, fragrant amine content therein is analyzed with GC-MS, and is quantified by internal standard method.Specific step is as follows:
(1) sample pre-treatments:
It samples according to the method for GB/T 5606. 1-2004 and GB/T 16447-2004 and adjusts 3R4F cigarette sample,
It traps cigarette mainstream smoke condensate and (10 cigarette mainstream smoke condensates is trapped under HCI suction mode, under ISO suction mode
Trap 20 cigarette mainstream smoke condensates), the filter disc after trapping is placed in 100 mL sample bottles, 60 mL are separately added into
5% HCL aqueous solution and 50 μ L mix internal standard, in 45 min of oscillation extraction on oscillator, whole extracting solution qualitative filter paper filterings
Afterwards, pH to 12 ~ 13 is adjusted with 4.0 mol/L NaOH solutions, adds 2 mL toluene and 2 g anhydrous sodium sulfates, liquid-liquid dispersions are vortexed
2 min are extracted, take out upper organic phase after 8000 r/min centrifugation, derive 40 min with 5 μ L heptafluorobutyric anhydrides (HFBA), with nothing
Sample prepare liquid is used as after water magnesium sulfate, N- propyl ethylenediamine (PSA) and the purification of C18 powder dispersive solid-phase extraction；
(2) standard working solution is prepared:
Prepare include the preparation of 9 kinds of aromatic amines and 6 kinds of deuterated interior target list mark stock solutions, 9 kinds of aromatic amines and 6 kinds it is deuterated in
The preparation of the mixed mark stock solution of target and the preparation of series standard working solution；
(3) GC-MS is measured:
Draw prepared series standard working solution injection GC-MS, with standard series peak area and internal standard peak area it
Compare its quality and establish equation of linear regression, sample prepare liquid is measured, measure the peak area of each target aromatic amine with it is interior
The ratio between peak area is marked, equation of linear regression is substituted into, respectively obtains the content of 9 kinds of aromatic amines in sample.
Detailed process is as follows for standard working solution preparation:
Single mark stock solution: the 9 kinds of aromatic amines and 6 kinds that mass concentration is 1 mg/mL are prepared respectively using methanol as solvent
Deuterated interior target list mark stock solution；
Mixed mark stock solution: 200 μ L ortho-aminotoluenes, meta-aminotoluene, para-totuidine are pipetted respectively；50 μ L naphthalidines, 2- naphthalene
Amine；20 μ L 2,6- dimethylanilines；Single mark stock solution of 10 μ L 3- aminobphenyls, 4- aminobphenyl, o-aminoanisole,
10 mL are settled to toluene, obtain the mixing stock solution of 9 kinds of aromatic amines；The deuterated interior target list mark of 6 kinds of 50 μ L is pipetted respectively
Stock solution is settled to 25 mL with toluene, obtains 6 kinds of deuterated interior targets that mass concentration is 4 mg/mL and mixes stock solution；
Series standard working solution: accurately pipette respectively 0.01 mL, 0.02 mL, 0.05 mL, 0.1 mL, 0.2 mL,
The mixing stock solution of 9 kinds of aromatic amines of 0.3 mL is separately added into 6 kinds of deuterated interior target mixing stock solutions of 50L, with dilution with toluene
It is settled to 2 mL, derivative 40 min of 5 μ L heptafluorobutyric anhydrides (HFBA), with anhydrous magnesium sulfate, N- propyl ethylenediamine (PSA) and C18
Series standard working solution is obtained after the purification of powder dispersive solid-phase extraction.
GC-MS analysis condition is as follows:
Chromatographic column: DB-35 elastic capillary-column, mm × 0.25 μm 30 m × 0.25；Injector temperature: 280 DEG C；
Ion source temperature: 230 DEG C；Transmission line temperature: 280 DEG C；Sample volume: 1 μ L；Splitless injecting samples；Carrier gas: helium, constant current mode, stream
Measure 0.8 mL/min；Temperature programming: then 60 DEG C of 2 min of holding rise to 140 DEG C with the rate of 10 DEG C/min, then with 4 DEG C/min
Rate rise to 190 DEG C, finally rise to 280 DEG C with the rate of 30 DEG C/min, keep 20 min；
Mass Spectrometry Conditions: transmission line temperature: 280 DEG C；Ionization mode: electron bombardment ionization source (EI)；Ionizing energy: 70 eV；Ion
Source temperature: 260 DEG C；Solvent delay: 8 min；It is scanned using choice ion pattern (SIM), 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 fragrance in a kind of cigarette mainstream flue gas
The gaschromatographic mass spectrometry rapid assay methods of amine.Mainly according to cigarette smoke sample the characteristics of, to liquid-liquid micro-extraction pre-treatment
Extraction solvent, salting-out agents of method etc. have carried out selection and optimization, and have investigated the influence of derivatization reagent dosage and cleanser.
(2) sample pretreatment process of this method is simple, quick, and analysis time is greatly saved.
(3) the reproducible of this method, the rate of recovery are high, the inspection of 9 kinds of aromatic amine burst sizes suitable for cigarette mainstream flue gas
It surveys.
Detailed description of the invention:
Fig. 1: measuring method flow chart of the present invention.
Fig. 2: (figure a is total ion current figure to the chromatogram of standard working solution；Scheming b is to extract ion figure).
Specific embodiment
Present invention combination example is described further, but is not the limitation present invention.
Example 1:
(1) instrument and reagent:
Thermo ISQ gas chromatography-mass spectrometry (Thermo Fisher company, the U.S.)；RM-200A rotating disc type is inhaled
Smoke machine (German Borgwaldt company)；Labnet VX-200 vortex mixed instrument (Labnet company, the U.S.)；Supercentrifuge (moral
Sigma company, state)；Milli-Q ultrapure water system (Millipore company, the U.S.).
Ortho-aminotoluene (o-TOL), meta-aminotoluene (m-TOL), para-totuidine (p-TOL), 2,6- dimethylaniline (2,6-
DMA), o-aminoanisole (o-ASD), naphthalidine (1-NA), 2- naphthylamines (2-NA), 3- aminobphenyl (3-ABP), 4- amino connection
Benzene (4-ABP), D9Ortho-aminotoluene (o-TOL-d9), D7O-aminoanisole (o-ASD-d7), D7Naphthalidine (1-NA-d7),
D7- 2- naphthylamines (2-NA-d7), D11- 2,6- dimethylaniline (2,6-DMA-d11), D9- 4- aminobphenyl (4-ABP-d9) (moral
Dr. Ehrensorfer company, state)；Toluene, n-hexane, t-butyl methyl ether (chromatographically pure, J. T. Baker company, the U.S.), hydrogen
Sodium oxide molybdena, sodium chloride, sodium sulphate (analyzing pure, Tianjin north Reagent Company), 3 kinds of d-SPE purification kits are respectively 150 mg
2 mL kits (5021) of anhydrous magnesium sulfate and 25 mg N- propyl ethylenediamines (PSA)；150 mg anhydrous magnesium sulfates, 50 mg
The 2 mL kits (5022) of PSA；2 mL kits (5122) of 150 mg anhydrous magnesium sulfates, 50 mg PSA and 50 mg C18
(Agilent company, the U.S.)；3R4F reference cigarette sample.
The comparison of three kinds of kits is preferably as follows: from the point of view of the color by purification front and back sample solution, through three kinds of purification reagents
The color of sample shoals after box processing, and GC-MS analysis the result shows that, although for o-ToL, m-ToL and p-ToL,
Three kinds of cleansers response to which that signal has certain decrease, but not significant, especially for 2,6-DMA, o-ASD, 1-NA, 2-
NA, 3-ABP, 4-ABP are substantially without influence.Therefore consider mainstream smoke constituents complexity, final experimental selection containing 150 mg without
The purification kit of water magnesium sulfate, 50 mg PSA and 50 mg C18 purifies sample.
(2) sample pre-treatments
It samples according to the method for GB/T 5606. 1-2004 and GB/T 16447-2004 and adjusts cigarette sample.HCI
10 cigarette mainstream smoke condensates are trapped under suction mode, trap 20 cigarette mainstream smoke condensates under ISO suction mode.
Filter disc after trapping is placed in 100 mL sample bottles, is separately added into 60 mL, 5% HCL aqueous solution and 50 μ L mixing
Mark is adjusted after 45 min of oscillation extraction on oscillator, whole extracting solution qualitative filter paper filterings with 4.0 mol/L NaOH solutions
PH to 12 ~ 13 adds 2 mL Extraction solvents and 2 g salting-out agents, after liquid-liquid dispersions extraction of ocean eddies 2 min, 8000 r/min centrifugation
Upper organic phase is taken out, derives 40 min with heptafluorobutyric anhydride (HFBA), with 150 mg anhydrous magnesium sulfates, 50 mg PSA and 50
GC-MS analysis is carried out after the purification of mg C18 dispersive solid-phase extraction.
Wherein extractant, salting-out agents, derivatization reagent and Solid phase extraction composition are optimized.As a result
When showing using toluene, t-butyl methyl ether, n-hexane as Extraction solvent, toluene extraction efficiency is best, therefore choosing toluene is to extract
Agent.When being separately added into sodium chloride and sodium sulphate to promote aromatic amine to be assigned in toluene by water phase, the effect of sodium sulphate is more preferable,
Therefore choosing sodium sulphate is salting-out agents.When investigating the influence of derivatization reagent, pentafluoropropionic anhydride and heptafluorobutyric anhydride difference are not
Greatly, but when using heptafluorobutyric anhydride as derivatization reagent, anti-interference ability is more preferable when 3-ABP and 4-ABP are detected, thus finally with
Heptafluorobutyric anhydride is derivatization reagent, and its dosage is optimized, the results showed that 5 μ L heptafluorobutyric anhydrides are enough to ensure that derivative
Change complete.
(3) preparation of standard working solution
The preparation of standard working solution mainly includes the preparation of 9 kinds of aromatic amines and 6 kinds of deuterated interior target list mark stock solutions, 9
The preparation of kind aromatic amine and the mixed mark stock solution of 6 kinds of deuterated interior targets and the preparation of series standard working solution, were specifically prepared
Journey is as previously mentioned, be not repeated herein.
(4) GC-MS analyzes result
Series standard working solution is subjected to GC-MS analysis, it is compared with standard series peak area and internal standard peak area
Quality establishes equation of linear regression.It is real that the rate of recovery is carried out to 3R4F cigarette mainstream flue gas under ISO suction mode using mark-on method
It tests, the detection limit of analysis method, horizontal replication 3 times of low middle high three mark-ons is calculated by signal-to-noise ratio S/N >=3.Method
The result (such as table 3) of evaluation shows the good (R of 9 kinds of aromatic amine linear relationships2> 0.998), the rate of recovery of 3 mark-on levels exists
Between 73.3% ~ 124.5%, relative standard deviation (RSD) is 0.2 ~ 9.6%, and detection limit (LOD) is 0.03 ~ 0.08 ng/cig.
ISO and HCI mode aspirates 9 kinds of aromatic amine measurement results in lower 3R4F cigarette mainstream flue gas and is shown in Table 4.
In addition, the measurement result of this method and the measurement result of traditional existing national standard method are compared, as a result
As shown in table 5, it is seen that except the measurement result of 2,6-DMA has outside different, this method and tradition side for remaining 8 kinds of aromatic amine
The consistency of method measurement result is preferable.Since the pretreatment process based on liquid-liquid micro-extraction of this method is simple, thus provide
A method of fast and accurately aromatic amine in main flume.
Claims (4)
1. a kind of method of 9 kinds of aromatic amines in GC-MS detection cigarette mainstream flue gas based on liquid-liquid micro-extraction, it is characterised in that:
The aromatic amine for trapping the release in main flume by cambridge filter first, is added internal standard, is obtained with aqueous hydrochloric acid solution to suction
Cambridge filter carry out mechanical shaking extraction, sodium hydrate aqueous solution is added, pH is adjusted to 12 ~ 13, a certain amount of extractant is added
Toluene, salting-out agents anhydrous sodium sulfate are shaked, and upper toluene layer is taken out after centrifugation, is performed the derivatization with heptafluorobutyric anhydride, are passed through
After dispersive solid-phase extraction purification, fragrant amine content therein is analyzed with GC-MS, and is quantified by internal standard method；
Specific step is as follows:
(1) sample pre-treatments:
It samples according to the method for GB/T 5606. 1-2004 and GB/T 16447-2004 and adjusts 3R4F cigarette sample, trap
Filter disc after trapping is placed in 100 mL sample bottles by cigarette mainstream smoke condensate, is separately added into 60 mL, 5% HCl/water
Solution and 50 μ L mix internal standard, after 45 min of oscillation extraction on oscillator, whole extracting solution qualitative filter paper filterings, with 4.0
Mol/L NaOH solution adjusts pH to 12 ~ 13, adds 2 mL toluene 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, derives 40 min with 5 μ L heptafluorobutyric anhydrides (HFBA), with anhydrous sulphur
Sample prepare liquid is used as after sour magnesium, N- propyl ethylenediamine (PSA) and the purification of C18 powder dispersive solid-phase extraction；
(2) standard working solution is prepared:
Prepare preparation, 9 kinds of aromatic amines and 6 kinds of deuterated interior targets including 9 kinds of aromatic amines and 6 kinds of deuterated interior target list mark stock solutions
The preparation of mixed mark stock solution and the preparation of series standard working solution, 6 kinds of deuterated internal standards specifically: o-aminoanisole-d7,
2,6- dimethylaniline-d11, ortho-aminotoluene-d9, naphthalidine-d7,2- naphthylamines-d7 and 4- aminobphenyl-d9；
(3) GC-MS is measured:
Prepared series standard working solution injection GC-MS is drawn, with comparing for standard series peak area and internal standard peak area
Its quality establishes equation of linear regression, is measured to sample prepare liquid, 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；
GC-MS analysis condition is as follows:
Chromatographic column: DB-35 elastic capillary-column, mm × 0.25 μm 30 m × 0.25；Injector temperature: 280 DEG C；Ion
Source temperature: 230 DEG C；Transmission line temperature: 280 DEG C；Sample volume: 1 μ L；Splitless injecting samples；Carrier gas: helium, constant current mode, flow
0.8 mL/min；Temperature programming: then 60 DEG C of 2 min of holding rise to 140 DEG C with the rate of 10 DEG C/min, then with 4 DEG C/min's
Rate rises to 190 DEG C, finally rises to 280 DEG C with the rate of 30 DEG C/min, keeps 20 min；
Mass Spectrometry Conditions: transmission line temperature: 280 DEG C；Ionization mode: electron bombardment ionization source (EI)；Ionizing energy: 70 eV；Ion source temperature
Degree: 260 DEG C；Solvent delay: 8 min；It is scanned using choice ion pattern (SIM).
2. according to the method described in claim 1, it is characterized by: 9 kinds of aromatic amines specifically: naphthalidine, 2- naphthylamines, 3- amino
Biphenyl, 4- aminobphenyl, o-aminoanisole, 2,6- dimethylaniline, ortho-aminotoluene, meta-aminotoluene, para-totuidine.
3. according to the method described in claim 1, it is characterized by: trapping cigarette mainstream smoke condensate when, HCI suction mode
10 cigarette mainstream smoke condensates of lower trapping trap 20 cigarette mainstream smoke condensates under ISO suction mode.
4. according to the method described in claim 1, it is characterized by: standard working solution is prepared, detailed process is as follows:
Single mark stock solution: preparing 9 kinds of aromatic amines that mass concentration is 1 mg/mL using methanol as solvent respectively and 6 kinds deuterated
Interior target list mark stock solution；
Mixed mark stock solution: 200 μ L ortho-aminotoluenes, meta-aminotoluene, para-totuidine are pipetted respectively；50 μ L naphthalidines, 2- naphthylamines；
20 μ L 2,6- dimethylanilines；Single mark stock solution of 10 μ L 3- aminobphenyls, 4- aminobphenyl, o-aminoanisole, with first
Benzene is settled to 10 mL, obtains the mixing stock solution of 9 kinds of aromatic amines；The deuterated interior target list mark deposit of 6 kinds of 50 μ L is 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 stock solution；
Series standard working solution: 0.01 mL, 0.02 mL, 0.05 mL, 0.1 mL, 0.2 mL, 0.3 mL are accurately pipetted respectively
9 kinds of aromatic amines mixing stock solution, 6 kinds of 50 μ L deuterated interior targets mixing stock solutions are separately added into, with dilution with toluene constant volume
To 2 mL, derivative 40 min of 5 μ L heptafluorobutyric anhydrides (HFBA), with anhydrous magnesium sulfate, N- propyl ethylenediamine (PSA) and C18 powder
Series standard working solution is obtained after dispersive solid-phase extraction purification.
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| CN108414661B (en) * | 2018-03-13 | 2020-04-21 | 中国医科大学 | Derivatization gas chromatography-mass spectrometry method for detecting ammonia content in biological sample |
| CN108982710B (en) * | 2018-09-28 | 2021-06-01 | 江苏德旺数码科技有限公司 | Method for detecting polycyclic aromatic hydrocarbon in dye |
| CN110749676B (en) * | 2019-10-30 | 2022-08-30 | 深圳天祥质量技术服务有限公司 | Method for detecting migration quantity of ethylenediamine and hexamethylenediamine in food contact material and product |
| CN111474261B (en) * | 2020-04-24 | 2023-02-24 | 山东省济南生态环境监测中心 | Method for measuring aniline in soil and sediment |
| CN115993414A (en) * | 2023-01-18 | 2023-04-21 | 中汽研汽车零部件检验中心(宁波)有限公司 | Method for determining amine substances of automobile nonmetallic material |
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