CN105675740A - Carbon isotope method for tracing aldehyde ketone pollutants - Google Patents

Carbon isotope method for tracing aldehyde ketone pollutants Download PDF

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CN105675740A
CN105675740A CN201511027563.0A CN201511027563A CN105675740A CN 105675740 A CN105675740 A CN 105675740A CN 201511027563 A CN201511027563 A CN 201511027563A CN 105675740 A CN105675740 A CN 105675740A
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aldehyde ketone
cysteamine
value
pollutant
reaction
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郭送军
陈梅
何晓朗
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Guangxi University
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    • 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
    • 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
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas 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
    • G01N2030/062—Preparation extracting sample from raw material

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Abstract

The invention discloses a carbon isotope method for tracing aldehyde ketone pollutants. The method is characterized in that sources of aldehyde ketone pollutants in atmosphere environment are judged according to occurrence of isotope fractionation or not and the difference of the carbon isotope ratio (delta<13>C value). An experiment result shows that the method has the advantages of good recurrence and high precision of a determination result, and effective overcoming of the defects of traditional concentration measurement methods (EPA TO-11A), can be used to determine the carbon isotope composition (delta<13>C value) of atmosphere aldehyde ketone pollutants in order to realize direct and accurate judgment of the sources of the atmosphere aldehyde ketone pollutants, can be used to trace the sources of the atmosphere aldehyde ketone pollutants as an effective way, is helpful for researching the formation mechanism of atmosphere organic pollution, and provides scientific bases for researches of the atmosphere organic environment pollution.

Description

The carbon isotope method of spike aldehyde ketone pollutant
Technical field
The invention belongs to aldehyde ketone pollutant monitoring analysis field in atmospheric environment, particularly relate to a kind of carbon isotope method of spike aldehyde ketone pollutant.
Background technology
At present, the concentration of aldehyde ketone pollutant in commonly used U.S. EPA TO-11A method detection air in the world, and adopt the method such as concentration proportion and correlation analysis, namely formaldehyde/acetaldehyde or acetaldehyde/acetone etc. judge the separate sources of the aldehyde ketone pollutant such as Formaldehyde in Atmosphere, acetaldehyde and acetone. But, the explanation in source is indirectly by this analysis method, simultaneously because ratio excursion is very big and unstable, the conclusion drawn is fuzzyyer. Nowadays air combined pollution event takes place frequently so that the volatile organic matters such as air aldehyde ketone pollutant receive significant attention, air aldehyde ketone pollutant in the urgent need to address source judges this difficult problem. Along with developing rapidly of gas chromatogram-burning-isotopic ratio mass spectrum (GC-C-IRMS) analytical technology, for using carbon isotope ratio spike air aldehyde ketone pollutant sources to lay a good foundation.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of carbon isotope method of aldehyde ketone pollutant of spike accurately and reliably, it is simple to directly judge its pollution source, provides scientific basis for the work of air organic environment Pollution Study.
For solving above-mentioned technical problem, the present invention by the following technical solutions: the carbon isotope method of spike aldehyde ketone pollutant, first pass through coating NaHSO3Silica gel sampling tube gather aldehyde ketone pollutant sample in air, then adopting cysteamine derivative reaction aldehyde ketone pollutant, recycling gas chromatogram-burning-isotopic ratio mass spectrum (GC-C-IRMS) measures cysteamine and the δ of aldehyde ketone-Cysteamine derivatives13C value, obtains the δ of aldehyde ketone pollutant in air finally according to isotope effect Theoretical Calculation13C value.
The carbon isotope method of above-mentioned spike aldehyde ketone pollutant, comprises the following steps:
(1) preparation aldehyde ketone and aldehyde ketone-Cysteamine derivatives standard sample
Take after 1mL aldehyde ketone solution joins and at least balance 1h in 5mL sample bottle, with the screw capping good seal with holes that can fill chromatography column feed materials pad; After the aldehyde ketone waiting amount of substance is reacted 24h with Mercaptamine in the aqueous solution that pH is 8～9, use CHCl3Extract, extract anhydrous Na2SO4Dried filtration, filtrate rotary evaporation at normal temperatures is concentrated into after completely;
(2) simulation reaction or atmospheric environment sampling
Simulation reaction: with high-purity N2After rinsing Teflon reaction bag, evacuate reaction bag with sampling pump;After aldehyde ketone gaseous sample after volatilization is injected reaction bag, with coating NaHSO3Sep-Pak silica gel sampling tube be connected with sampling pump and be acquired, flow 2L/min;
Atmospheric environment is sampled: by sampling pump and coating NaHSO3Sep-Pak silica gel sampling tube be connected carry out atmospheric sample collection;
(3) process of sample
After simulation reaction, sampling tube sample adds 20 μ L150 μ g/ μ L cysteamine solution with the 2mLpH HCl solution eluting being 2 after 5mL scale test tube, 60 DEG C of heating in water bath 20min, regulates pH value 8～9 with 200 μ g/ μ LNaOH solution; With the CHCl of 2mL after normal-temperature reaction 24h3Extract 3 times, extract anhydrous Na2SO4Dried filtration, filtrate is at normal temperatures with high-purity N2Seal to be analyzed after being concentrated into 200 μ L;
(4) δ of Mercaptamine, aldehyde ketone and derivant thereof is measured13C value
Mercaptamine δ13C value adopts DELTAplusXL isotope-ratio mass spectrometer (EA-IRMS) measures;
Aldehyde ketone and aldehyde ketone-Cysteamine derivatives δ13The mensuration of C value adopts gas chromatogram-burning-isotopic ratio mass spectrum (GC-C-IRMS);
(5) aldehyde ketone theoretical value is calculated
By comparing the derivant δ being measured out by GC-C-IRMS13C value and the theoretical value calculated, judge whether there occurs isotope fractionation in course of reaction.
Theoretical value in step (5) calculates by below equation:
δ13CAldehyde ketone=δ13CAldehyde ketone-NaHSO3(1)
δ13CAldehyde ketone-Cysteamine derivatives=fAldehyde ketoneδ13CAldehyde ketone+fCysteamineδ13CCysteamine(2)
S2 Aldehyde ketone=(fCysteamine/fAldehyde ketone)2S2 Cysteamine+(1/fAldehyde ketone)2S2 Aldehyde ketone-Cysteamine derivatives(3)
Wherein, fAldehyde ketoneWith fCysteamineThe respectively mark shared by this material carbon atom in derivant, and fAldehyde ketone+fCysteamine=1, (as acetaldehyde, fAcetaldehyde=1/2); It addition, air aldehyde ketone pollutant δ13The standard deviation of C value is calculated by equation (3).
For aldehyde ketone pollutant sources recognition methods Problems existing in existing atmospheric environment, inventor utilizes gas chromatogram/burning/isotopic ratio (GC-C-IRMS) technology, establishing a kind of carbon isotope method of spike aldehyde ketone pollutant, according to whether there is isotope fractionation and carbon isotope ratio (δ in this method13C value) difference judge the source of aldehyde ketone pollutant in atmospheric environment. Test result indicate that, the deviation range that in the present invention, Mercaptamine, aldehyde ketone and aldehyde ketone-Cysteamine derivatives repeatedly measure is 0.09～0.21%, and favorable reproducibility; The method is used to measure the δ of air aldehyde ketone pollutant13During C, the deviation of its theoretical value and measured value is respectively less than 0.50 ‰, in the precision allowed band of instrument (± 0.50 ‰), namely measures aldehyde ketone pollutant δ in this way13Do not occur isotope fractionation in the process of C value during derivative reaction, formula the aldehyde ketone theoretical value calculated just can represent the δ of aldehyde ketone in real atmosphere13C value. Visible, measurement result favorable reproducibility of the present invention, precision is high, it is possible to efficiently against the defect existing for traditional levels measurement method (EPATO-11A), for measuring the carbon isotope composition (δ of air aldehyde ketone pollutant13C value) it is capable of directly accurately judging the source of air aldehyde ketone pollutant, can as a kind of effective means of spike air aldehyde ketone pollutant sources, contribute to the formation mechenism of research Air Organic Pollution, provide scientific basis for the work of air organic environment Pollution Study.
Accompanying drawing explanation
Fig. 1 is the Technology Roadmap that the application present invention carries out carbon isotope analysis.
Detailed description of the invention
Fig. 1 is shown that the application present invention and carries out the Technology Roadmap of carbon isotope analysis, further illustrates the present invention below in conjunction with embodiment 1.
Embodiment 1
This example selects the aldehyde ketone (acetaldehyde, similar example of the enforcement of other aldehyde ketone pollutant) of simulation concentration known to carry out sampling and gather the experiment of Real Atmosphere environmental sample and measures its carbon isotope composition respectively.
Main Analysis instrument: Germany Finnigan company DELTAplusXL isotope-ratio mass spectrometer (EA-IRMS); GV company of Britain gas chromatogram-burning-isotope-ratio mass spectrometer (GC-C-IRMS)
(1) preparation acetaldehyde and acetaldehyde-Cysteamine derivatives standard sample
Take after 1mL acetaldehyde solution joins and at least balance 1h in 5mL sample bottle, to be analyzed with the screw capping good seal with holes that can fill chromatography column feed materials pad; After the acetaldehyde waiting amount of substance is reacted 24h with Mercaptamine (purity 97%) in the aqueous solution that pH is 8～9, use CHCl3(analytical pure, secondary uses after heavily steaming) extracts, extract anhydrous Na2SO4Dried filtration, filtrate rotary evaporation at normal temperatures is concentrated into after completely to be analyzed;
(2) simulation experiment sampling and atmospheric environment sampling
A () simulation experiment is sampled: with high-purity N2(99.99%) rinse after Teflon reaction bag, with gas sampling pump depletion reaction bag so that it is in without other gaseous impurity; Then squeeze into the acetaldehyde solution (analytical pure, A1 and A2 producer) of certain volume concentration by sample introduction needle from injection port, open N2Valve, acetaldehyde is at N2Effect under volatilization and in reaction bag, when reaction bag is also completely filled with N2Time close N2Valve, with coating NaHSO3Sep-Pak silica gel sampling tube be connected with sampling pump and be acquired, flow 2L/min;
B () atmospheric environment is sampled: by sampling pump and coating NaHSO3Sep-Pak silica gel sampling tube be connected and carry out atmospheric sample collection, sampled point is Guangzhou geochemical investigation institute and Zhaoqing Dinghu Hill.
(3) process of sample
After sampling terminates, sample cell is successively with masking foil and soaked NaHSO3Filter paper wrap, seal with Teflon packaging bag and be stored in the refrigerator of 4 DEG C, all test a Field blank after sampling blank with laboratory, test result shows without blank interference. Sampling tube sample with HCl solution (pH is for the 2) eluting of 2mL in 5mL scale test tube, add 20 μ L cysteamine solution (150 μ g/ μ L) after 60 DEG C of heating in water bath 20min, be finally added thereto to about 100 μ LNaOH solution (200 μ g/ μ L) and regulate pH value 8～9; With the CHCl of 2mL after normal-temperature reaction 24h3Extract 3 times, extract anhydrous Na2SO4Dried filtration, filtrate is at normal temperatures with high-purity N2The refrigerator being stored in 4 DEG C is sealed to be analyzed after being concentrated into 200 μ L;
(4) δ of Mercaptamine, acetaldehyde and derivant thereof is measured13C value
Mercaptamine δ13C value adopts DELTAplusXL isotope-ratio mass spectrometer (EA-IRMS) measures, and is undertaken by following operation: sample enters CEEA1112CN/S analyser after putting into automatic sampler, at O2Burning in combustion furnace in 960 DEG C under effect, using CuO as catalyst, the gas after burning is loaded in reduction furnace by high-purity He, enters chromatographic column and separate at 650 DEG C after reducing for catalyst with Cu, the gas (CO after separation2) enter DELTA by Conflo III adapter (Finnigan)plusXL isotope-ratio mass spectrometer; The δ provided with laboratory before each sample analysis13The carbon black of C=36.91 ‰ assesses accuracy of instrument and stability.
The δ of acetaldehyde standard sample13C pH-value determination pH is undertaken by following operation: adopts GC/C/IRMS, takes the headspace gas 20 μ L sample introduction of acetaldehyde solution with 5mLHamilton gas sampling pin, with known δ13The CO of C=26.65 ‰2Gas is interior mark, and isotope groups becomes the CH of 36.30 ‰4The precision of standard specimen detecting instrument and stability, concrete testing conditions is, CuO furnace temperature: 880 DEG C, Cu reduction furnace temperature: 580 DEG C, GC and junction, combustion furnace temperature: 300 DEG C, split ratio: 50:1, chromatographic column HP-PLOTQ (30m × 0.32mm × 20 μm), carrier gas (He) flow velocity: 1.5mL/min, injector temperature: 200 DEG C, column temperature: 180 DEG C of constant temperature.
The δ of acetaldehyde-Cysteamine derivatives13C pH-value determination pH is undertaken by following operation: adopt GC-C-IRMS, with known isotopic ratio δ13The CO of C=26.65 ‰2As reference gas, with carbon isotope ratio respectively 28.60 ‰, 26.70 ‰, 28.60 ‰ containing C10, C11, C12N-alkane and carbon isotope ratio be the C of 30.50 ‰13Compound GV-mix standard specimen (methyl-deaconate is provided by GVInstruments, UK) assesses precision and the stability of instrument. Testing conditions is, inside fill out combustion furnace (oxidation furnace) temperature of CuO/Ni/Pt: 850 DEG C, Cu reduction furnace temperature: 580 DEG C, GC is arranged with junction, combustion furnace temperature: 300 DEG C, Splitless injecting samples, and chromatographic column is HP-5MS (30m × 0.32mm × 0.25 μm), carrier gas (He) flow velocity: 1.5mL/min, injector temperature: 200 DEG C, chromatographic column heating schedule is after 50 DEG C of reservation 2min, then rises to 85 DEG C with 3 DEG C/min.
(5) aldehyde ketone theoretical value is calculated
Theoretical according to isotope effect, the isotope fractionation in chemical reaction depends on that first order reaction determining reaction rate, if the generation of chemical bond that is not connected with carbon atom of this grade and fracture, obvious isotope fractionation would not occur; In this derivatization reaction, the carbon atom of cysteamine is not engaged in course of reaction, and therefore, the isotope effect of this reaction is only relevant with the carbon atom of aldehyde ketone, allows aldehyde ketone all participate in reaction would not to produce obvious isotope fractionation as long as ensureing that cysteamine is excessive; Isotope effect before and after reacting under this condition meets equation (1-2):
δ13CAldehyde ketone=δ13CAldehyde ketone-NaHSO3(1)
δ13CAldehyde ketone-Cysteamine derivatives=fAldehyde ketoneδ13CAldehyde ketone+fCysteamineδ13CCysteamine(2)
Wherein, fAldehyde ketoneWith fCysteamineThe respectively mark shared by this material carbon atom in derivant, and fAldehyde ketone+fCysteamine=1, (as acetaldehyde, fAcetaldehyde=1/2); It addition, air aldehyde ketone pollutant δ13The standard deviation of C value is calculated by equation (3).
S2 Aldehyde ketone=(fCysteamine/fAldehyde ketone)2S2 Cysteamine+(1/fAldehyde ketone)2S2 Aldehyde ketone-Cysteamine derivatives(3)
By comparing the derivant δ being measured out by GC-C-IRMS13The theoretical value that C value and (by equation (1-3)) calculate, judges whether there occurs isotope fractionation in course of reaction.
The carbon isotope effect result of the acetaldehyde simulation experiment of different manufacturers is listed in table 1.
Carbon isotope effect result (δ in table 1 acetaldehyde simulation experiment course of reaction13C value)
Every kind of sample all being done and repeatedly analyzes, their Standard deviation-Range is less than 0.50%, and the Standard deviation-Range of corresponding derivant measured value is less than 0.50 ‰; The δ of derivant13The deviation range of C measured value and theoretical value is again smaller than 0.50 ‰, and result above is all in accuracy of instrument scope (± 0.50 ‰), and measured value repeatedly is respectively provided with good repeatability, illustrates that carbon isotope fractionation does not occur the inventive method.
Carbon isotope composition (the δ of acetaldehyde in the atmospheric environment samples gathered in this example13C value) such as table 2.
Carbon isotope effect result (δ in table 2 atmospheric environment sampling process13C value)
Known by table 2, in the air sample that gathered emission source is different, acetaldehyde δ in its atmospheric environment13The excursion of C value is variant, such as forest air and urban atmosphere in this example, illustrates that analysis of carbon isotope compositions method of the present invention can as a kind of effective means identifying air aldehyde ketone pollutant sources.
GC-C-IRMS technical Analysis is adopted to measure test result indicate that of aldehyde ketone pollutant (such as acetaldehyde) isotope effect: with NaHSO3Carbon isotope fractionation, experimental data favorable reproducibility will not occur during aldehyde ketone pollutant in silica gel sampling tube collection and cysteamine derivatization air, and measurement accuracy is high, and the carbon isotope composition of air aldehyde ketone pollutant can be calculated by mass balance equation and obtain.The inventive method measure air aldehyde ketone pollutant carbon isotope composition it is shown that to have the carbon isotope composition of aldehyde ketone pollutant in the atmospheric environment of different emission source variant. Therefore, the present invention can as a kind of effective means of aldehyde ketone pollutant sources identification in research air, and the research for air aldehyde ketone pollutant provides technical support.

Claims (3)

1. the carbon isotope method of spike aldehyde ketone pollutant, it is characterised in that: first pass through coating NaHSO3Silica gel sampling tube gather aldehyde ketone pollutant sample in air, then adopt cysteamine derivative reaction aldehyde ketone pollutant, recycling gas chromatogram-burning-isotopic ratio mass spectrum measures cysteamine and the δ of aldehyde ketone-Cysteamine derivatives13C value, obtains the δ of aldehyde ketone pollutant in air finally according to isotope effect Theoretical Calculation13C value.
2. the carbon isotope method of spike aldehyde ketone pollutant according to claim 1, it is characterised in that comprise the following steps:
(1) preparation aldehyde ketone and aldehyde ketone-Cysteamine derivatives standard sample
Take after 1mL aldehyde ketone solution joins and at least balance 1h in 5mL sample bottle, with the screw capping good seal with holes that can fill chromatography column feed materials pad; After the aldehyde ketone waiting amount of substance is reacted 24h with Mercaptamine in the aqueous solution that pH is 8～9, use CHCl3Extract, extract anhydrous Na2SO4Dried filtration, filtrate rotary evaporation at normal temperatures is concentrated into after completely;
(2) simulation reaction or atmospheric environment sampling
Simulation reaction: with high-purity N2After rinsing Teflon reaction bag, evacuate reaction bag with sampling pump; After aldehyde ketone gaseous sample after volatilization is injected reaction bag, with coating NaHSO3Sep-Pak silica gel sampling tube be connected with sampling pump and be acquired, flow 2L/min;
Atmospheric environment is sampled: by sampling pump and coating NaHSO3Sep-Pak silica gel sampling tube be connected carry out atmospheric sample collection; (3) process of sample
After simulation reaction, sampling tube sample adds 20 μ L150 μ g/ μ L cysteamine solution with the 2mLpH HCl solution eluting being 2 after 5mL scale test tube, 60 DEG C of heating in water bath 20min, regulates pH value 8～9 with 200 μ g/ μ LNaOH solution; With the CHCl of 2mL after normal-temperature reaction 24h3Extract 3 times, extract anhydrous Na2SO4Dried filtration, filtrate is at normal temperatures with high-purity N2Seal to be analyzed after being concentrated into 200 μ L;
(4) δ of Mercaptamine, aldehyde ketone and derivant thereof is measured13C value
Mercaptamine δ13C value adopts DELTAplusXL isotope-ratio mass spectrometer measures;
Aldehyde ketone and aldehyde ketone-Cysteamine derivatives δ13The mensuration of C value adopts gas chromatogram-burning-isotopic ratio mass spectrum;
(5) aldehyde ketone theoretical value is calculated
By comparing the derivant δ being measured out by GC-C-IRMS13C value and the theoretical value calculated, judge whether there occurs isotope fractionation in course of reaction.
3. the carbon isotope method of spike aldehyde ketone pollutant according to claim 2, it is characterised in that the theoretical value in step (5) calculates by below equation:
δ13CAldehyde ketone=δ13CAldehyde ketone-NaHSO3(1)
δ13CAldehyde ketone-Cysteamine derivatives=fAldehyde ketoneδ13CAldehyde ketone+fCysteamineδ13CCysteamine(2)
S2 Aldehyde ketone=(fCysteamine/fAldehyde ketone)2S2 Cysteamine+(1/fAldehyde ketone)2S2 Aldehyde ketone-Cysteamine derivatives(3)
Wherein, fAldehyde ketoneWith fCysteamineThe respectively mark shared by this material carbon atom in derivant, and fAldehyde ketone+fCysteamine=1; It addition, air aldehyde ketone pollutant δ13The standard deviation of C value is calculated by equation (3).
CN201511027563.0A 2015-02-04 2015-12-31 Carbon isotope method for tracing aldehyde ketone pollutants Pending CN105675740A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106124602A (en) * 2016-06-17 2016-11-16 中国科学院地质与地球物理研究所 A kind of geology rock sample nitrogen isotope measure method
CN111044552A (en) * 2019-12-31 2020-04-21 核工业北京地质研究院 Method for recovering heat storage temperature based on silicon isotope fractionation relation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
郭送军等: "大气丙酮碳同位素组成测定方法的研究", 《分析化学》 *
郭送军等: "大气乙醛碳同位素分析方法的研究", 《环境监测管理与技术》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106124602A (en) * 2016-06-17 2016-11-16 中国科学院地质与地球物理研究所 A kind of geology rock sample nitrogen isotope measure method
CN111044552A (en) * 2019-12-31 2020-04-21 核工业北京地质研究院 Method for recovering heat storage temperature based on silicon isotope fractionation relation

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Application publication date: 20160615