CN110187037B - System and method for measuring content of 57 volatile organic compounds in ambient air - Google Patents
System and method for measuring content of 57 volatile organic compounds in ambient air Download PDFInfo
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Abstract
A system and method for measuring the content of 57 volatile organic compounds in ambient air comprises a four-way valve, a gas chromatograph and a three-stage cold trap preconcentrator; four ports of the four-way valve are respectively connected with the pre-separation column, the first re-separation column, the second re-separation column and the helium gas source; the gas chromatograph is provided with a flame ionization detector and a mass spectrum detector. The method comprises the following steps: (1) preparing mixed standard use gas; (2) preparing internal standard use gas; (3) collecting an ambient air sample; (4) establishing a standard curve of the target component; (5) taking an ambient air sample to be detected, pre-concentrating the ambient air sample through a three-stage cold trap to remove interfering substances, focusing the ambient air sample, allowing the focused ambient air sample to enter a mass spectrum detector for gas chromatography mass spectrum analysis, obtaining the content of each component according to the peak area and the standard curve established in the step (4), and calculating the concentration of the sample to be detected according to the sample introduction volume of the sample to be detected. The invention can simultaneously analyze two detectors by one-time sample injection, is simple and effective, and avoids the influence of interference substances on the measurement result.
Description
Technical Field
The invention relates to a method for measuring volatile organic compounds (57 types) in ambient air, which combines gas chromatography-hydrogen flame ionization detection/mass spectrometry detection and belongs to the technical field of volatile organic compound measurement.
Background
57 Volatile Organic Compounds (VOCs) are a branch of the volatile organic compounds, and the molecular structure only comprises two sources of carbon and hydrogenA carbon atom number of C2～C12Including alkenes, alkanes, aromatics, and alkynes, are considered ozone generating Precursors (PAMS) due to their strong photochemical activity. Many countries use as monitoring indicators substances that are present in large amounts in urban ambient air and that play a major role in ozone generation, i.e. substances from the original PAMS list. The 57 volatile organic components are shown in the following table:
the physical and chemical properties of 57 volatile organic compounds are greatly different from ethylene with the lowest boiling point (-104 ℃) to dodecane with the highest boiling point (217 ℃), the boiling point span reaches more than 300 ℃, and the simultaneous enrichment and analysis are difficult; and the boiling point and the molecular weight of the ethylene, the ethane, the acetylene and the propane are low, so that the difficulty of chromatographic column separation is increased. The technology for analyzing 57 ozone precursor substances in the atmosphere, which is applied more at present, is a commercial real-time online monitoring system, and mainly comprises the following steps: 1. respectively collecting C by two sets of sampling systems2～C4Component (A) and (C)5～C12The components are simultaneously analyzed by two sets of gas chromatographic analysis systems; 2. using a center-cutting technique, C2～C4The components are analyzed by a flame ionization detector, C5The high carbon component is analyzed by a mass spectrometer or flame ionization detector.
In 57 volatile organic compounds, the isomers are more, if gas chromatography-flame ionization detection analysis is simply adopted, a plurality of pairs of co-effluent component pairs exist, and all compounds cannot be accurately quantified; if mass spectrometry analysis is adopted, cold column temperature sample injection is needed, and the sensitivity of ethylene, acetylene and ethane is low.
The existing standard analysis methods for measuring the volatile organic compounds in the ambient air (such as HJ759-2015 'measuring tank sampling/gas chromatography-mass spectrometry' for the volatile organic compounds in the ambient air and HJ644-2013 'measuring adsorption tube sampling-thermal desorption/gas chromatography-mass spectrometry' for the volatile organic compounds in the ambient air) cannot meet the requirement of full component analysis of 57 ozone precursor organic compounds with large boiling point span, especially on 3 components of ethane, ethylene and acetylene with low molecular weight and strong volatility.
The invention discloses a CN108627604A discloses a general device for detecting all components of volatile organic compounds in ambient air, which belongs to environment-friendly detection equipment, and particularly relates to a general device for detecting all components of volatile organic compounds in ambient air. Although the device can make the sample pass through one-time sample introduction and analyze all volatile organic compounds simultaneously, the structure is complex. The structure is complicated, and the installation and the maintenance are difficult. The simultaneous analysis of multi-component samples by gas chromatography-flame ionization detectors cannot avoid the influence of interfering substances, and sometimes false positive results are difficult to judge.
CN1719249 discloses a method for measuring volatile organic compounds in air. The method comprises the steps of collecting air at normal temperature by using a sampling tube filled with poly (2, 6-diphenyl-p-phenylene ether), and adsorbing volatile organic compounds in the sampling tube; and (3) placing the sampling tube in a first-stage thermal desorption instrument for thermal desorption, and enabling the volatile organic compounds to enter a gas chromatograph for separation and determination along with the carrier gas in an online combined manner from the thermal desorption instrument. The invention can make the capillary chromatographic column maintain high separation (resolution) capability to the spectral peak, and can not cause spectral peak broadening. The on-line combination technology of the first-stage thermal desorption instrument and the gas chromatograph achieves the effect of a secondary structure with a cold trap, and the peak shape is equivalent to that of direct sample introduction. The desorption furnace of the first-level thermal desorption instrument is connected with the sample inlet of the chromatograph on line, and the sample completely enters the chromatograph through single thermal desorption, so that the method has high sensitivity, and the sensitivity is at least 100 times higher than that of a method for taking 1 ml of sample by desorbing 100ml in the Chinese national standard GB 11737-89. The method has limitation in analysis of target components, and only poly (2, 6-diphenyl-p-phenylene ether) can be analyzedEnriched fraction. Analyzable of C only6The above component, C2-C5The components cannot be analyzed, and the full component analysis cannot be realized; the sample introduction mode has no sample focusing link, and peak tailing is easy to occur.
Disclosure of Invention
Aiming at the defects of the existing 57 volatile organic compound monitoring technology, the invention provides a system and a method for measuring the content of 57 volatile organic compounds in ambient air, which can effectively avoid the possibility that false positive results are easy to appear in multi-component simultaneous detection and realize the simultaneous analysis of 57 ozone precursor organic compounds by one sample introduction and one set of system.
The invention relates to a system for measuring the content of 57 volatile organic compounds in ambient air, which adopts the following technical scheme:
the measuring system comprises a four-way valve, a gas chromatograph and a three-stage cold trap preconcentrator; four ports of the four-way valve are respectively connected with the pre-separation column, the first re-separation column, the second re-separation column and the helium gas source; the gas chromatograph is provided with a flame ionization detector (FID detector) and a mass spectrum detector (MS detector), the pre-separation column, the first re-separation column and the second re-separation column are chromatographic columns, the pre-separation column is connected with a three-stage cold trap pre-concentration instrument, the first re-separation column is connected with the flame ionization detector, the second re-separation column is connected with the mass spectrum detector, and the three-stage cold trap pre-concentration instrument is connected with a sample injector and is connected with a helium gas source through a sample inlet of the gas chromatograph.
The four-way valve has the heating and heat preservation functions, and the heating temperature is 80-120 ℃.
And an auxiliary electronic pressure sensor (EPC) is arranged on a connecting pipe of the four-way valve and the helium gas source to control the gas pressure.
And an electronic pressure sensor is arranged at the sample inlet of the gas chromatograph. The auxiliary electronic pressure sensor and the gas chromatograph sample inlet electronic pressure sensor detect helium pressure, and the helium is used as assisting gas for switching the four-way valve.
The pre-separation column was a DB-1 capillary column (100% dimethylpolysiloxane capillary column) of size 60m x 0.32mm x 1.0 μm; the first repeated separation column is a rulerGAS-Pro capillary column of 30 mm by 0.32mm size for C separation2～C4Preparing components; the second re-separation column was a DB-1 capillary column (100% dimethylpolysiloxane capillary column) of size 30m x 0.32mm x 1.0 μm for separation of C5～C12And (4) components.
The method for measuring the content of 57 volatile organic compounds in the ambient air by the system comprises the following steps:
(1) preparation of mixing standard use gas:
diluting the standard mixed gas (the concentration is 1.00 mu mol/mol) with high-purity nitrogen (the purity is more than or equal to 99.999%) to obtain mixed standard use gas with the concentration of 2.00nmol/mol, and storing the mixed standard use gas into a first vacuum sampling tank (the internal pressure of the sampling tank is less than 10 Pa);
the dilution process in the step (2) is as follows: firstly, diluting standard mixed gas and high-purity nitrogen to intermediate standard use gas of 40.0nmol/mol in a volume ratio of 1: 25; then, the intermediate standard use gas of 40.0nmol/mol and high-purity nitrogen gas were diluted to a concentration of 2.00nmol/mol at a volume ratio of 1:20 to prepare a mixed standard use gas.
(2) Gas was used for internal standard preparation:
an internal standard gas containing four components of bromochloromethane, p-bromofluorobenzene, 1, 2-difluorobenzene and chlorobenzene-d 5 and having a concentration of 1.00 mu mol/mol is diluted to an internal standard use gas having a concentration of 5.00nmol/mol by using high-purity nitrogen (purity is more than or equal to 99.999%), and the internal standard use gas is stored in a second vacuum sampling tank (the internal pressure of the sampling tank is less than 10 Pa).
The dilution process in the step (3) is as follows: the internal standard gas used was prepared by diluting an internal standard gas and high-purity nitrogen gas at a volume ratio of 1:10 to an intermediate standard gas used at a concentration of 100.0nmol/mol, and then diluting the intermediate standard gas used at a volume ratio of 1:20 to a concentration of 5.00 nmol/mol.
(3) Collecting an ambient air sample:
collecting an ambient air sample by instantaneous sampling or constant flow sampling as described below;
instantaneous sampling: bringing a third vacuum sampling tank (the internal pressure of the sampling tank is less than 10Pa) to a sampling point, installing a filter on the third vacuum sampling tank, opening a sample injection valve of the third vacuum sampling tank to start sampling, and closing the sampling valve after the internal pressure of the third vacuum sampling tank is consistent with the atmospheric pressure of the sampling point;
constant flow sampling: bringing a third vacuum sampling tank (the internal pressure of the sampling tank is less than 10Pa) to a sampling point, mounting a constant-flow sampler and a filter on the third vacuum sampling tank, opening a sample injection valve of the third vacuum sampling tank to start sampling, and closing the sampling valve after the internal pressure of the third vacuum sampling tank is consistent with the atmospheric pressure of the sampling point;
(4) drawing a standard curve:
a mixed standard use gas (standard use gas of the same concentration) prepared by analyzing a set of step (2) of increasing volume gradient; simultaneously, internal standard gas prepared in the step (3) is taken, interfering substances are removed through three-stage cold trap preconcentration (realized by adopting a three-stage cold trap preconcentrator), and the internal standard gas enters a mass spectrum detector for gas chromatography mass spectrometry after being focused, so that a standard curve of a target component is established; (the internal standard gas and the mixed standard gas are simultaneously analyzed, the three-stage cold trap preconcentrator firstly collects the mixed standard gas, then collects the internal standard gas, finally focuses simultaneously and enters a capillary column for separation and analysis)
The gradient increment means that the volumes of the gas used for the mixing standard are 50ml, 100ml, 400ml, 800ml and 1000ml, corresponding to concentrations of 1.00nmol/mol, 2.00nmol/mol, 8.00nmol/mol, 16.0nmol/mol and 20.0nmol/mol at each concentration point when the volume of the sample to be analyzed is 100 ml; the internal standard was used with a gas take-up volume of 100 ml.
(5) Taking an ambient air sample to be detected, carrying out tertiary cold trap preconcentration through a tertiary cold trap preconcentrator, removing interfering substances, carrying out gas chromatography-mass spectrometry on the focused ambient air sample entering a mass spectrometry detector, obtaining the content of each component according to the peak area and the standard curve established in the step (4), and calculating the concentration of the sample to be detected according to the sample introduction volume of the sample to be detected. The volume of the ambient air sample to be measured is at least 20ml (the minimum volume should not be less than 20ml, adjusted according to the sample concentration).
The conditions of the three-stage cold trap preconcentration in the step (4) and the step (5) are as follows:
primary cold trap: trapping temperature: -120 ℃; collecting flow rate: 60 ml/min; resolving the preheating temperature: 0 ℃; resolving temperature: 10 ℃; baking temperature: baking time at 150 ℃: for 10 minutes. The type of primary cold trap is a trap filled with glass beads and TENAX. Tenax is a porous polymer resin widely used for collecting volatile or semi-volatile substances in gases, liquids and solids;
secondary cold trap: the trapping temperature is-40 ℃; collecting flow rate: 10 ml/min, trapping volume: 40 ml; the resolving temperature is 160 ℃; analysis time: 3 minutes; the baking temperature is 190 ℃; baking time: for 10 minutes. The secondary cold trap type is a trap filled with TENAX;
and (3) third-stage cold trap: the trapping temperature is-175 ℃; the sample injection time is 2 minutes, and the baking time is 10 minutes.
The conditions of the gas chromatography-mass spectrometry in the step (4) and the step (5) are as follows:
a column temperature program comprising a pre-separation column, a first re-separation column, and a second re-separation column: holding at-10 deg.C for 6min, heating to 10 deg.C at 15 deg.C/min, heating to 150 deg.C at 4 deg.C/min, heating to 240 deg.C at 15 deg.C/min, and holding for 2 min; flow rate of the chromatographic column: 2.5 mL/min; gas chromatograph injection port temperature: 220 ℃; the flame ionization detector (FID detector) temperature was 300 ℃. The temperature rise of the chromatographic column is realized by a gas chromatographic column incubator, and the temperature of a sample inlet of the gas chromatograph is controlled by the gas chromatograph at 220 ℃. The carrier gas pressure of the three-stage cold well preconcentrator is controlled by EPC at the gas chromatography sample inlet.
The gas chromatography mass spectrometry in the step (4) and the step (5) comprises the following steps:
the four-way valve is closed in the initial state, the pre-separation column is communicated with the first re-separation column, the second re-separation column is communicated with a helium gas source, the three-stage cold trap pre-concentrator enriches the ambient air sample, the ambient air sample enters the pre-separation column for separation, and the four-way valve shunts the ambient air sample to the first re-separation column for separation C2～C4The components enter a flame ionization detector; wait for C2～C4After the last component on the pre-separation column flows out, the four-way valve is opened, the pre-separation column is communicated with the second re-separation column, and the first re-separation column is used for re-separatingThe separation column is communicated with a helium gas source, and the environmental air sample is separated by the pre-separation column and then is switched to the second re-separation column to separate the rest C5～C12A component, analyzed by a mass detector; after the analysis is completed, the four-way valve is adjusted to a closed state.
The method is used for measuring the content of the ozone precursor volatile organic compounds in the environmental air sample, adopts a three-stage cold trap concentration technology to enrich target components, switches the target components through a four-way valve, and analyzes C through a flame ionization detector2～C4Low carbon component, mass spectrometry analysis of the rest C5～C12A high carbon component. Not only ensures the effective enrichment of ethane, ethylene, acetylene, propane and the like, but also can improve the analysis sensitivity; the mass spectrum detector analyzes the rest high-carbon components, so that the possibility that false positive results are easy to appear in the simultaneous detection of multiple components can be effectively avoided. Realizes one-time sample injection, and one set of system simultaneously analyzes 57 ozone precursor organic matters and obtains good practical effect.
The invention adopts a valve switching technology to shunt volatile organic compounds with large physical and chemical property differences to two capillary columns with different polarities for separation, a flame ionization detector analyzes low-carbon components, and a mass spectrometry detector analyzes the rest high-carbon components. The invention simply and effectively realizes the purpose of simultaneously analyzing two detectors by one-time sample introduction, and effectively avoids the influence of interference substances on the measurement result. Compared with the prior art, the four-way valve provided by the invention has the advantages that the sample cutting mode is simple to operate, convenient to install, economic and cheap; the method has high sensitivity and good reproducibility.
Drawings
FIG. 1 is a flow chart showing the four-way valve in the measurement system of the present invention in a closed state.
FIG. 2 is a flow chart showing the four-way valve in the measurement system of the present invention in an open state.
FIG. 3 is C of measurement2～C4A low carbon component gas chromatogram.
FIG. 4 shows measured C5～C12High carbon component selection ion flow diagrams.
In fig. 1 and 2: the first is a pre-separation column, the second is a first re-separation column, and the third is a second re-separation column.
In the curves of fig. 3 and 4: 1. ethane, 2. ethylene, 3. acetylene, 4. propane, 5. propylene, 6. isobutane, 7. n-butane, 8.1-butene, 9. trans-2-butene, 10. cis-2-butene, 11.2-methylbutane, 12.1-pentene, 13. n-pentane, 14. isoprene, 15. trans-2-pentene, 16. cis-2-pentene, 17.2, 2-dimethylbutane, 18. cyclopentane, 19.2, 3-dimethylbutane, 20.2-methylpentane, 21.3-methylpentane, 22.1-hexene, 23. n-hexane, 24. methylcyclopentane, 25.2, 4-dimethylpentane, 26. benzene, 27. cyclohexane, 28.2-methylhexane, 29.2, 3-dimethylpentane, 30.3-methylhexane, 31.2,2, 4-trimethylpentane, 32. heptane, 33. methylcyclohexane, 34.2,3, 4-trimethylpentane, 35. toluene, 36.2-methylheptane, 37.3-methylheptane, 38. octane, 39. ethylbenzene, 40 and 41. m/p-xylene, 42. styrene, 43. o-xylene, 44. nonane, 45. cumene, 46. propylbenzene, 47. m-ethyltoluene, 48. p-ethyltoluene, 49. mesitylene, 50. o-ethyltoluene, 51.1,2, 4-trimethylbenzene, 52. decane, 53.1,2, 3-trimethylbenzene, 54. m-diethylbenzene, 55. p-diethylbenzene, 56. undecane, 57. dodecane, 58. bromochloromethane, 59.1, 2-difluorobenzene, 60. chlorobenzene-d 5, 61. p-bromofluorobenzene.
Detailed Description
The invention uses three-stage cold trap to pre-concentrate and enrich the sample, and the sample is switched by a four-way valve, and the flame ionization detector measures C2～C4Component, Mass spectrometric Detector C5～C12And (4) components. Aiming at realizing the purpose that the target components in the same sample are cut to different detectors for analysis through a four-way valve, and C is2～C4The low carbon component is separated by a strong polarity capillary column and is analyzed by a flame ionization detector with higher sensitivity, and the rest C is5～C12The components are separated by a nonpolar capillary column and analyzed by a mass spectrum detector, so that the component pairs can be accurately and quantitatively co-flowed, and the influence of interfering substances can be avoided.
The inventor explores a proper analysis condition by optimizing the switching time of the four-way valve and optimizing the selection of a capillary column, the flow of a chromatographic column and the pretreatment concentration enrichment condition.
The measuring system of the invention is shown in figure 1 and figure 2, and comprises a four-way valve, a flame ionization detector (FID detector), a mass spectrum detector (MS detector and a three-stage cold trap preconcentrator, wherein the four-way valve has the heating and heat preservation functions, the existing commercial products are directly purchased, the heating temperature is 80-120 ℃, four ports of the four-way valve are respectively connected with a pre-separation column (I), a first re-separation column (II), a second re-separation column (III) and a helium gas source, an auxiliary electronic pressure sensor (EPC) is arranged on a connecting pipe with the helium gas source to monitor the air pressure, the pre-separation column (I), the first re-separation column (II) and the second re-separation column (III) are chromatographic columns, the pre-separation column (I) is connected with the three-stage cold trap preconcentrator, the first re-separation column (II) is connected with the flame ionization detector, the second re-separation column (III) is connected with the mass spectrum detector, and is connected with a helium gas source through a gas chromatograph sample inlet, and an electronic pressure sensor (the gas chromatograph sample inlet electronic pressure sensor in figure 1) is arranged at the gas chromatograph sample inlet. And the auxiliary electronic pressure sensor and the gas chromatography sample inlet electronic pressure sensor are both connected with a helium gas source, and the helium gas is used as the power-assisted gas for switching the four-way valve. The three-stage cold trap pre-concentrator sucks the collected ambient air sample through an automatic sample injector, removes interfering substances, and finally focuses and concentrates.
Pre-separation column (i) is a DB-1 capillary column with the size of 60m x 0.32mm x 1.0 μm. First second separation column for C2～C4The component was a GAS-Pro capillary column of size 30m x 0.32 mm. Second secondary separation column C for separating C5～C12The composition was a DB-1 capillary column of size 30m x 0.32mm x 1.0 μm.
The four-way valve is closed in the initial state, the pre-separation column is communicated with the first secondary separation column, the second secondary separation column is communicated with the helium gas source, as shown in figure 1, a three-stage cold trap pre-concentration instrument adopts a three-stage cold trap pre-concentration instrument to pre-concentrate an ambient air sample, the sample enters the pre-separation column to be separated after being heated and analyzed, and C2～C4The components (ethane, ethylene, acetylene, propylene, propane, n-butane, isobutane, 1-butene, trans-2-butene, cis-2-butene) are branched off in a four-way valve toThe first secondary separation column is separated and then enters the FID detector for analysis, and the second secondary separation column is provided with carrier gas (helium gas) through an auxiliary electronic pressure sensor. After 12 minutes, wait for C2～C4After the last component on the pre-separation column flows out, the four-way valve is opened, the pre-separation column is communicated with the second re-separation column, the first re-separation column is communicated with a helium gas source, as shown in fig. 2, an ambient air sample is separated by the pre-separation column and then switched to the second re-separation column to separate the rest components, the ambient air sample is analyzed by a mass spectrum detector, and the first re-separation column is used for providing carrier gas through an auxiliary electronic pressure sensor (EPC). After the analysis is completed, the four-way valve is adjusted to a closed state.
The conditions of the three-stage cold trap pre-concentration are as follows: keeping the temperature at-10 ℃ for 6min, heating to 10 ℃ at 15 ℃/min, heating to 150 ℃ at 4 ℃/min, heating to 240 ℃ at 15 ℃/min, and keeping the temperature for 2 min, wherein the flow rate of the chromatographic column is 2.5 mL/min. Sample inlet temperature: 220 ℃; the flame ionization detector (FID detector) temperature was 300 ℃.
Example 1
This example carried out the analysis of 57 volatile organic compounds in ambient air
(1) Preparation of mixed standard use gas
Diluting a standard mixed gas with the concentration of 1.00 mu mol/mol with high-purity nitrogen (more than or equal to 99.999%) by a gas dilution device to an intermediate standard use gas of 40.0nmol/mol in a volume ratio of 1: 25; and performing secondary dilution on the intermediate standard use gas of 40.0nmol/mol and high-purity nitrogen (more than or equal to 99.999%) according to the volume ratio of 1:20 to the concentration of 2.00nmol/mol to obtain a mixed standard use gas, and storing the mixed standard use gas into a clean and vacuumized sampling tank (a first vacuum sampling tank). The sampling tank is heated, humidified, cleaned and vacuumized (< 10Pa) by a cleaning device. The gas diluting device adopts the prior devices with various structures, and belongs to the prior art.
(2) Gas for preparing internal standard
Diluting an internal standard gas containing bromochloromethane, p-bromofluorobenzene, 1, 2-difluorobenzene and chlorobenzene-d 5 with the concentration of 1.0 mu mol/mol and high-purity nitrogen (more than or equal to 99.999%) in a volume ratio of 1:10 to an intermediate standard gas used with the concentration of 100.0nmol/mol through a gas diluting device, diluting the intermediate standard gas used with the high-purity nitrogen (more than or equal to 99.999%) in a volume ratio of 1:20 to the concentration of 5.00nmol/mol through the gas diluting device to prepare the internal standard gas used, storing the internal standard gas used until cleaning and vacuumizing (less than 10Pa) to a sampling tank (a second vacuum sampling tank).
(3) Collecting samples:
the ambient air sample is taken by one of two means:
instantaneous sampling: bringing a third vacuum sampling tank (the internal pressure of the sampling tank is less than 10Pa) to a sampling point, mounting a filter on the third vacuum sampling tank, opening a sampling inlet valve (rotating anticlockwise) of the third vacuum sampling tank to start sampling, closing the sampling inlet valve after the internal pressure of the third vacuum sampling tank is consistent with the atmospheric pressure of the sampling point, and sealing by using a sealing cap;
constant flow sampling: and (3) bringing the third vacuum sampling tank to a sampling point, mounting a constant-flow sampler and a filter on the third vacuum sampling tank, opening a sample valve (rotating anticlockwise) of the third vacuum sampling tank to start sampling, closing the sample valve after the pressure in the third vacuum sampling tank is consistent with the atmospheric pressure of the sampling point, and sealing by using a sealing cap.
(4) Drawing of standard curve
The quantitative method includes an external standard method and an internal standard method. The external standard method is a standard curve established according to the correlation of the response and the content of the target object; the internal standard method is a curve established by taking the ratio of the response value of a target object to the response value of an internal standard object as a vertical coordinate and the ratio of the content of the target object to the content of the internal standard object as a horizontal coordinate. Mass spectrometry is generally quantified by internal standard methods.
The targets are the 57 components of the assay, each component being a target. Gas chromatography is a gas chromatography flame ionization detector, C analyzed in the present method2-C4Preparing components; the mass spectrometry is gas chromatography mass spectrometry, which is the same gas chromatograph as the gas chromatography, and the detector is a mass spectrometry detector. One-time sample introduction is realized through valve switching, and the two detectors analyze different components.
As shown in figure 1, the three-stage cold trap pre-concentration instrument is used for separationThe mixing standard used gas of 50ml, 100ml, 200ml, 400ml, 800ml and 1000ml, and the internal standard used gas of 100 ml. Removing interfering substances and focusing by a three-stage cold trap preconcentrator, switching by a four-way valve, separating by a first repeated separation column to realize analysis C by a flame ionization detector (FID detector)2～C4Establishing an external standard curve according to the peak area and content of a target object by using components (ethane, ethylene, acetylene, propylene, propane, isobutane, 1-butene, n-butane, trans-2-butene and cis-2-butene); the rest of the component (C)5～C12Component) is separated by a second re-separation column and then analyzed by a mass spectrum detector, and an internal standard curve of the target object is established according to the content of the target object, the quantitative ion peak area, the relative response factor and the quantitative ion peak area of an internal standard object (used by the internal standard). The chromatograms are shown in FIGS. 3 and 4. FIG. 3 is a chromatogram of the components of the established external standard curve, and FIG. 4 is a chromatogram of the components of the established internal standard curve.
(5) Ambient air sample analysis
An automatic sampler takes 100.0ml of an ambient air sample (the minimum volume is not less than 20ml according to the sample concentration adjustment) and 50.0ml of an internal standard substance, a three-stage cold trap preconcentrator removes interfering substances, the interfering substances are concentrated and focused, the mixture is separated by a capillary column, and a flame ionization detector analyzes ethane, ethylene, acetylene, propylene, propane, isobutane, 1-butene, n-butane, trans-2-butene and cis-2-butene; the mass detector analyzes the remaining components. And (4) dividing the content of the target object searched according to the standard curve by the sample injection volume to obtain the concentration of the target component. The concentration of the target component in 57 in ambient air is shown in the following table.
Concentration units of 57 volatile organic compounds in ambient air: nmol/mol
Example 2
This example demonstrates a methodological study of the method of the invention.
Preparing mixed standard use gas with the concentration of 0.5nmol/mol, wherein the sample volume is 100ml, preparing 7 groups in parallel according to the method of the invention, and calculating the detection limit (MDL) of each component method according to the formula (1); preparing standard gases with low, medium and high concentrations of 2.00nmol/mol, 10.0nmol/mol and 18.0nmol/mol by using high-purity nitrogen, wherein the sample volume is 100ml, carrying out 6 times of method precision experiments in parallel according to the method of the invention, and carrying out accuracy determination according to blank standard adding calculation and standard adding recovery. Detecting the limit and determining the offline condition by the method; the precision and accuracy results are shown in Table 3.
MDL＝t(n-1,0.99)×S (1)
In the formula: n is the number of sample determinations; t is the t distribution (one-sided) with a confidence of 99% when the degree of freedom is n-1; s is the standard deviation of n measurements.
Method detection limit and assay lower limit
The result shows that the detection limit of the method for 57 target compounds is between 0.15 and 1.82nmol/mol, the lower limit of the detection is between 0.56 and 7.26nmol/mol, and the method has high sensitivity.
Precision and accuracy measurement results of target compounds with the addition concentration of 2.00nmol/mol in group 1
Precision and accuracy measurement results of target compounds with the addition concentration of 10.0nmol/mol in group 2
Precision and accuracy measurement results of target compounds in group 3 with addition concentration of 18.0nmpl/mol
The Relative Standard Deviation (RSD) of the concentration levels of the three groups is less than 10.8 percent, and the recovery rate of the added standard is between 75.3 and 119 percent, which shows that the method has high sensitivity and good precision. The valve switching technique can be successfully applied to the determination of 57 volatile organic compounds in ambient air.
Claims (4)
1. A method for measuring the contents of 57 volatile organic compounds in ambient air is characterized in that,
the measuring method uses a measuring system for the content of 57 volatile organic compounds in ambient air, and the measuring system comprises a four-way valve, a gas chromatograph and a three-stage cold trap preconcentrator; four ports of the four-way valve are respectively connected with the pre-separation column, the first re-separation column, the second re-separation column and the helium gas source; the gas chromatograph is provided with a flame ionization detector and a mass spectrum detector, the pre-separation column is connected with a three-stage cold trap preconcentrator, the first re-separation column is connected with the flame ionization detector, the second re-separation column is connected with the mass spectrum detector, and the three-stage cold trap preconcentrator is connected with a sample injector and a helium gas source;
the determination method comprises the following steps:
(1) preparation of mixing standard use gas:
diluting a standard mixed gas with the concentration of 1.00 mu mol/mol with high-purity nitrogen with the concentration of more than or equal to 99.999 percent to an intermediate standard use gas with the volume ratio of 1:25 to 40.0nmol/mol through a gas diluting device; secondly diluting the intermediate standard use gas of 40.0nmol/mol and high-purity nitrogen with the concentration of more than or equal to 99.999 percent to the concentration of 2.00nmol/mol according to the volume ratio of 1:20 to prepare a mixed standard use gas, storing the mixed standard use gas until the mixed standard use gas is cleaned and pumped to a first vacuum sampling tank;
(2) gas was used for internal standard preparation:
diluting an internal standard gas containing bromochloromethane, p-bromofluorobenzene, 1, 2-difluorobenzene and chlorobenzene-d 5 and having a concentration of 1.0 mu mol/mol and a high-purity nitrogen gas having a concentration of more than or equal to 99.999% to an intermediate standard use gas having a concentration of 100.0nmol/mol through a gas diluting device according to a volume ratio of 1:10, diluting the intermediate standard use gas and the high-purity nitrogen gas having a concentration of more than or equal to 99.999% to a concentration of 5.00nmol/mol through the gas diluting device according to a volume ratio of 1:20 to prepare an internal standard use gas, storing the internal standard use gas into a second vacuum sampling tank which is clean and vacuumized;
(3) collecting an ambient air sample:
collecting an ambient air sample by either instantaneous sampling or constant flow sampling;
instantaneous sampling: bringing a third vacuum sampling tank to a sampling point, wherein a filter is arranged on the third vacuum sampling tank, opening a sample injection valve of the third vacuum sampling tank to start sampling, and closing the sampling valve after the pressure in the third vacuum sampling tank is consistent with the atmospheric pressure of the sampling point;
constant flow sampling: bringing a third vacuum sampling tank to a sampling point, mounting a constant-flow sampler and a filter on the third vacuum sampling tank, opening a sample injection valve of the third vacuum sampling tank to start sampling, and closing the sampling valve after the pressure in the third vacuum sampling tank is consistent with the atmospheric pressure of the sampling point;
(4) drawing a standard curve:
using gas by analyzing a set of mixing criteria prepared in step (2) with increasing volume gradient; meanwhile, internal standard gas prepared in the step (3) is taken, interfering substances are removed through three-stage cold trap preconcentration, and gas chromatography analysis is carried out after focusing to establish a standard curve of a target component;
(5) taking an ambient air sample to be detected, carrying out three-stage cold trap preconcentration through a three-stage cold trap preconcentrator, removing interfering substances, carrying out gas chromatography analysis after focusing, obtaining the content of each component according to the peak area and the standard curve established in the step (4), and calculating the concentration of the sample to be detected according to the sample introduction volume of the sample to be detected;
the conditions of the gas chromatography in the step (4) and the step (5) are as follows:
a column temperature program comprising a pre-separation column, a first re-separation column, and a second re-separation column: holding at-10 deg.C for 6min, heating to 10 deg.C at 15 deg.C/min, heating to 150 deg.C at 4 deg.C/min, heating to 240 deg.C at 15 deg.C/min, and holding for 2 min; flow rate of the chromatographic column: 2.5 mL/min; gas chromatograph injection port temperature: 220 ℃; the temperature of the flame ionization detector is 300 ℃; the temperature rise of the chromatographic column is realized by a gas chromatographic column incubator, and the temperature of a sample inlet of the gas chromatograph is controlled by the gas chromatograph at 220 ℃; the carrier gas pressure of the three-stage cold trap preconcentrator is controlled by EPC at the gas chromatography sample inlet;
the four-way valve has the heating and heat preservation functions, and the heating temperature is 80-120 ℃; the pre-separation column is a DB-1 capillary column with the size of 60m x 0.32mm x 1.0 mu m; the first re-separation column was a GAS-Pro capillary column of size 30m x 0.32mm for separation of C2～C4Preparing components; the second re-separation column was a DB-1 capillary column of size 30m x 0.32mm x 1.0 μm for separation of C5～C12Preparing components;
the four-way valve is closed in the initial state, the pre-separation column is communicated with the first re-separation column, the second re-separation column is communicated with the helium gas source, the three-stage cold trap pre-concentrator enriches the ambient air sample, the ambient air sample enters the pre-separation column for separation, and the four-stage cold trap pre-concentrator enriches the ambient air sample and the helium gas sampleThe valve shunts to the first repeated separation column for separation C2～C4The components enter a flame ionization detector; wait for C2～C4After the last component on the pre-separation column flows out, the four-way valve is opened, the pre-separation column is communicated with the second re-separation column, the first re-separation column is communicated with a helium gas source, and the environmental air sample is separated by the pre-separation column and then is switched to the second re-separation column to separate the rest C5～C12A component, analyzed by a mass detector; after the analysis is finished, the four-way valve is adjusted to a closed state;
the 57 volatile organic components are shown in the following table:
2. the method according to claim 1, wherein the dilution in step (3) is performed by: the internal standard gas used was prepared by diluting an internal standard gas and high-purity nitrogen gas at a volume ratio of 1:10 to an intermediate standard gas used at a concentration of 100.0nmol/mol, and then diluting the intermediate standard gas used at a volume ratio of 1:20 to a concentration of 5.00 nmol/mol.
3. The assay method according to claim 1, wherein the gradient is gradually increased by volume of the mixing standard use gas of 50ml, 100ml, 400ml, 800ml and 1000ml, corresponding to concentrations of 1.00nmol/mol, 2.00nmol/mol, 8.00nmol/mol, 16.0nmol/mol and 20.0nmol/mol at each concentration point when the volume of the sample to be analyzed is 100 ml; the internal standard was used with a gas take-up volume of 100 ml.
4. The method according to claim 1, wherein the conditions for the three-stage cold trap preconcentration in the steps (4) and (5) are as follows:
primary cold trap: trapping temperature: -120 ℃; collecting flow rate: 60 ml/min; resolving the preheating temperature: 0 ℃; resolving temperature: 10 ℃; baking temperature: baking time at 150 ℃:10 minutes; the type of the primary cold trap is a trap filled with glass beads and TENAX; tenax is a porous polymer resin;
secondary cold trap: the trapping temperature is-40 ℃; collecting flow rate: 10 ml/min, trapping volume: 40 ml; the resolving temperature is 160 ℃; analysis time: 3 minutes; the baking temperature is 190 ℃; baking time: 10 minutes; the secondary cold trap type is a trap filled with TENAX;
and (3) third-stage cold trap: the trapping temperature is-175 ℃; the sample injection time is 2 minutes, and the baking time is 10 minutes.
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