CN111289632A - Micro-column polarity gradient separation and purification and carbon isotope detection method for polycyclic aromatic hydrocarbon - Google Patents
Micro-column polarity gradient separation and purification and carbon isotope detection method for polycyclic aromatic hydrocarbon Download PDFInfo
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- CN111289632A CN111289632A CN201811497230.8A CN201811497230A CN111289632A CN 111289632 A CN111289632 A CN 111289632A CN 201811497230 A CN201811497230 A CN 201811497230A CN 111289632 A CN111289632 A CN 111289632A
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- 238000000926 separation method Methods 0.000 title claims abstract description 28
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 27
- 238000000746 purification Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 14
- 238000001514 detection method Methods 0.000 title claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 25
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000741 silica gel Substances 0.000 claims abstract description 10
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 10
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 8
- 238000010828 elution Methods 0.000 claims abstract description 7
- 150000002632 lipids Chemical class 0.000 claims abstract description 5
- 239000002689 soil Substances 0.000 claims abstract description 5
- 238000012360 testing method Methods 0.000 claims description 21
- 239000003480 eluent Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 230000005526 G1 to G0 transition Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000001346 gas chromatography-isotope ratio mass spectrometry Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
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Abstract
A polycyclic aromatic hydrocarbon separation and purification and carbon stable isotope detection method based on micro-column polarity gradient is characterized in that total lipid components are extracted from a soil sample, and polycyclic aromatic hydrocarbon components are obtained through a primary silica gel chromatographic column; then transferring the polycyclic aromatic hydrocarbon component to a chromatographic column, and obtaining aromatic hydrocarbon components with different ring numbers by differential elution to realize separation and purification; and finally, performing gas chromatography-mass spectrometry and gas chromatography-isotope mass spectrometry on the aromatic hydrocarbon components with different ring numbers in sequence to realize accurate determination of the monomer isotope. The method can realize the accurate determination of the polycyclic aromatic hydrocarbon monomer molecular carbon isotope in the atmospheric organic pollutants.
Description
Technical Field
The invention relates to a technology in the field of environmental monitoring, in particular to a method for micro-column polarity gradient separation and purification and carbon isotope detection of polycyclic aromatic hydrocarbon.
Background
In the determination technology of the carbon isotopes of the monomer molecules of the polycyclic aromatic hydrocarbon, if purification and separation are not carried out, complex compounds which cannot be identified are often shown on a chromatogram map, so that background signals are seriously interfered, and the phenomena of co-overflow caused by more polycyclic aromatic hydrocarbon isomers are serious, so that the deviation of the isotope ratio of a target compound and a true value is increased finally.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for micro-column polarity gradient separation and purification of polycyclic aromatic hydrocarbon and carbon isotope detection, which establishes a set of unified standard easy to implement under the experimental conditions of sampling amount, the types of chromatographic fillers, the proportion of eluting solvents and the like, has good separation and purification effects, high repeatability and strong practicability, and thus realizes the accurate determination of the carbon isotope in the polycyclic aromatic hydrocarbon monomer molecule.
The invention is realized by the following technical scheme:
the invention relates to a method for micro-column polarity gradient separation and purification and carbon isotope detection of polycyclic aromatic hydrocarbon, which comprises the steps of extracting a total lipid component from a soil sample, and carrying out primary silica gel chromatography to obtain a polycyclic aromatic hydrocarbon component; then transferring the polycyclic aromatic hydrocarbon component to a chromatographic column, and obtaining aromatic hydrocarbon components with different ring numbers by differential elution to realize separation and purification; and finally, performing gas chromatography-mass spectrometry and gas chromatography-isotope mass spectrometry on the aromatic hydrocarbon components with different ring numbers in sequence to realize accurate determination of the monomer isotope.
The transferring to the chromatographic column refers to: taking polycyclic aromatic hydrocarbon components, utilizing a chromatographic column with the cross section inner diameter of about 4mm, loading 2mg of silica gel and alumina as a stationary phase, and finally taking aromatic hydrocarbon components with the diameter of more than 1mg to transfer to the chromatographic column.
The differential elution refers to: and (3) collecting and removing aromatic hydrocarbon components with different ring numbers of the complex compound background through organic solvent eluents with different volumes and different polarities.
The accurate determination of the monomer isotope is to analyze the aromatic hydrocarbon components with different ring numbers by gas chromatography-mass spectrometry test and determine whether the aromatic hydrocarbon components pass the standard of the monomer isotope analysis after confirming the signal intensity, the co-overflow condition and the background clearance degree of the complex compound; and when the monomer isotope passes through the standard of the monomer isotope analysis, carrying out secondary distinguishing elution by using an organic solvent eluent, and then carrying out separation and purification and gas chromatography-mass spectrometry test analysis again until the monomer isotope passes through the standard of the monomer isotope analysis to carry out gas chromatography-isotope mass spectrometry test.
The organic solvent eluent comprises n-hexane, benzene and dichloromethane solution, and organic solvents with different polarities are obtained through different proportions of the three organic solvents.
Technical effects
Compared with the prior art, the method aims at the occurrence characteristics of polycyclic aromatic hydrocarbon in the aerosol sample, the sample demand is more than 1mg of aromatic hydrocarbon component, the experimental time is about 30min, 100% separation of American EPA optimal control substances and removal of the compound background which is complicated to the maximum extent are ensured, and the testing precision of the carbon isotope of the monomer reaches less than +/-0.5 per mill.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a schematic diagram of an example gas chromatography-mass spectrometry test;
FIG. 3 is a schematic diagram of an example GC-MS test.
Detailed Description
As shown in fig. 1, the present embodiment includes the following steps:
step 1) obtaining total lipid components in the soil sample to be detected through atmospheric organic pollution by a Soxhlet extraction method.
And 2) preliminarily separating the total lipid component into saturated hydrocarbon, polycyclic aromatic hydrocarbon and non-hydrocarbon components through preliminary silica gel chromatography.
The preliminary silica gel chromatography adopts 100-mesh silica gel, and the silica gel loading amount of the silica gel chromatography column is as follows: the diameter was 0.5cm and the length was 6 cm.
And 3) taking the polycyclic aromatic hydrocarbon component, loading 2mg of silica gel and alumina serving as stationary phases by using a chromatographic column with the cross section inner diameter of about 4mm, and transferring the aromatic hydrocarbon component of more than 1mg to the chromatographic column.
And 4) collecting aromatic hydrocarbon components with different ring numbers and background of complex compounds removed through organic solvent eluents (n-hexane, benzene and dichloromethane solutions with different proportions) with different volumes and different polarities, and realizing separation and purification.
The organic solvent eluent comprises n-hexane, benzene and dichloromethane, and the proportion of the organic solvent eluent can be adjusted according to the sample condition.
And 5) carrying out gas chromatography-mass spectrometry on the aromatic hydrocarbon component to confirm the signal intensity, the co-overflow condition and the background removal degree of the complex compound, and then further judging whether the aromatic hydrocarbon component passes the standard of monomer isotope analysis.
The judgment standard is as follows: whether the signal intensity meets the isotope test standard or not, the co-overflow condition is basically not existed, and the background of the complex is basically eliminated.
And 6) correcting the polarity intensity of the organic solvent eluent in the separation and purification process according to the particularity of the aromatic hydrocarbon components which are not judged, and performing separation and purification and gas chromatography-mass spectrometry test and analysis again until the aromatic hydrocarbon components pass the standard of monomer isotope analysis.
The correction is as follows: depending on the separation effect, if the strongly polar component falls into the separated sample, the polarity of the eluent is suitably reduced; if the less polar component falls into the separated sample, the polarity of the eluent is suitably increased.
The gas chromatography-mass spectrometry test preferably adopts Agilent 5977A gas chromatography-mass spectrometry, the column model is DB-1MS fused silica column (60m x 0.32mm i.d., film thickness: 0.25 μm), and the temperature-raising program is as follows: keeping the temperature at 35 ℃ for 5min, then raising the temperature to 295 ℃ at the speed of 3 ℃/min, and keeping the temperature for 35 min.
And 7) carrying out corresponding gas chromatography-isotope mass spectrometry test on the separated and purified aromatic hydrocarbon components to obtain monomer molecular carbon isotope data of each polycyclic aromatic hydrocarbon component.
The gas chromatography-isotope mass spectrometry test preferably adopts Thermo-Fisher GC-IRMS (MAT 253) gas chromatography-isotope mass spectrometry, the model of the column is DB-5fused silica column (60m multiplied by 0.32mm i.d., filmthickness: 0.25 μm), and the temperature rise program is as follows: keeping the temperature at 35 ℃ for 5min, then raising the temperature to 295 ℃ at the speed of 3 ℃/min, and keeping the temperature for 35 min.
As shown in fig. 2, the test sample separation effect test and peak identification of the polycyclic aromatic hydrocarbon component: by the method for measuring the gas chromatography-mass spectrometry of the soil sample to be measured, the complex compound background is basically eliminated after separation, the co-overflow effect is not obvious except for individual peaks, and the isotope measurement requirement is met.
As shown in fig. 3, the polycyclic aromatic hydrocarbon monomer carbon isotope determination of the test sample: the polycyclic aromatic hydrocarbon monomer stable carbon isotope determination is carried out on a test sample, wherein the separation of some peaks cannot be completely separated (peaks 4+5, 6+7, 8+9) due to the too close nature, and then only the isotope value after the two peaks are combined can be obtained. The obtained isotope value has good repeatability, the standard deviation is between 0.05 and 0.4 per mill, and the measurement requirement of the monomer isotope is met.
In conclusion, the method needs less polycyclic aromatic hydrocarbon (the sample demand is more than 1mg of total aromatic hydrocarbon components), consumes short time (about 1 hour for separation experiments), has good separation and purification effects and high repeatability, and has strong practicability.
The foregoing embodiments may be modified in many different ways by those skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A polycyclic aromatic hydrocarbon separation and purification and carbon stable isotope detection method based on micro-column polarity gradient is characterized in that a polycyclic aromatic hydrocarbon component is obtained by extracting a total lipid component from a soil sample and passing through a primary silica gel chromatographic column; then transferring the polycyclic aromatic hydrocarbon component to a chromatographic column, and obtaining aromatic hydrocarbon components with different ring numbers by differential elution to realize separation and purification; and finally, performing gas chromatography-mass spectrometry and gas chromatography-isotope mass spectrometry on the aromatic hydrocarbon components with different ring numbers in sequence to realize accurate determination of the monomer isotope.
2. The method of claim 1, wherein said transferring to a chromatography column comprises: taking polycyclic aromatic hydrocarbon components, utilizing a chromatographic column with the cross section inner diameter of about 4mm, loading 2mg of silica gel and alumina as a stationary phase, and finally taking aromatic hydrocarbon components with the diameter of more than 1mg to transfer to the chromatographic column.
3. The method of claim 1, wherein said differential elution is: and (3) collecting and removing aromatic hydrocarbon components with different ring numbers of the complex compound background through organic solvent eluents with different volumes and different polarities.
4. The method as claimed in claim 1, wherein the monomer isotope is accurately determined by determining whether the standard of monomer isotope analysis is passed after analyzing aromatic hydrocarbon components with different ring numbers by gas chromatography-mass spectrometry and confirming the signal intensity, co-overflow condition and background clearance degree of complex compounds; and when the monomer isotope passes through the standard of the monomer isotope analysis, carrying out secondary distinguishing elution by using an organic solvent eluent, and then carrying out separation and purification and gas chromatography-mass spectrometry test analysis again until the monomer isotope passes through the standard of the monomer isotope analysis to carry out gas chromatography-isotope mass spectrometry test.
5. The method as claimed in claim 3 or 4, wherein the organic solvent eluent comprises n-hexane, benzene and dichloromethane, and organic solvents with different polarities are obtained by different ratios of the three organic solvents.
6. The method as claimed in claim 1, wherein the preliminary silica gel chromatography is performed by using 100 mesh silica gel, and the silica gel column is loaded with silica gel in an amount of: the diameter was 0.5cm and the length was 6 cm.
7. The method according to claim 1 or 4, wherein the separation and purification are: after the aromatic hydrocarbon component is tested by gas chromatography-mass spectrometry to confirm the signal intensity, the co-overflow condition and the background clearance degree of the complex compound, whether the signal intensity meets the isotope test standard or not is further judged, the co-overflow condition is basically absent, and the background of the complex compound is basically eliminated;
and correcting the polarity intensity of the organic solvent eluent in the separation and purification process according to the particularity of the aromatic hydrocarbon components which do not pass the judgment, and carrying out separation and purification and gas chromatography-mass spectrometry test analysis again until the aromatic hydrocarbon components pass the standard of monomer isotope analysis.
8. The method of claim 7, wherein said modifying comprises: depending on the separation effect, if the strongly polar component falls into the separated sample, the polarity of the eluent is suitably reduced; if the less polar component falls into the separated sample, the polarity of the eluent is suitably increased.
9. The method of claim 1, wherein the gc-ms test is performed with a temperature profile of: keeping the temperature at 35 ℃ for 5min, then raising the temperature to 295 ℃ at the speed of 3 ℃/min, and keeping the temperature for 35 min.
10. The method of claim 1, wherein the GC-MS test is performed at a temperature programmed to: keeping the temperature at 35 ℃ for 5min, then raising the temperature to 295 ℃ at the speed of 3 ℃/min, and keeping the temperature for 35 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113075346A (en) * | 2021-04-01 | 2021-07-06 | 天津师范大学 | Gas chromatography separation analysis method based on aromatic macrocycle, molecular cage and pillar quinone and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105548421A (en) * | 2015-12-07 | 2016-05-04 | 中国石油天然气集团公司 | Analysis method for polycyclic aromatic hydrocarbon content and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105548421A (en) * | 2015-12-07 | 2016-05-04 | 中国石油天然气集团公司 | Analysis method for polycyclic aromatic hydrocarbon content and application thereof |
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| TOMOAKI OKUDA ET AL.: "Separation of PAHs in Enviromental samples by use of solid-phase extraction system for carbon isotope analysis", 《J.MASS.SPECTROM.SOC.JPN.》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113075346A (en) * | 2021-04-01 | 2021-07-06 | 天津师范大学 | Gas chromatography separation analysis method based on aromatic macrocycle, molecular cage and pillar quinone and application |
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