CN117741028A - Miniaturized chromatographic device, atmospheric organic matter measuring system and measuring method - Google Patents
Miniaturized chromatographic device, atmospheric organic matter measuring system and measuring method Download PDFInfo
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Abstract
The application provides a miniaturized chromatographic device, wherein, including chromatographic column and synchronous heating device, synchronous heating device is with non-contact mode directly or indirectly right the chromatographic column heats, the chromatographic column is metal capillary column or quartz capillary column. The miniaturized chromatographic device capable of realizing uniform heating and rapid separation of substances is developed and integrated with the multiple ion source mass spectrum detector, a mutually-supplemented direct, fine and composite online measuring system of atmospheric substances can be formed, rapid separation and identification can be performed on the atmospheric substances in a targeted manner while rapid measurement is met, and technical support is provided for accurate tracing and management and control of the atmosphere.
Description
Technical Field
The application relates to the technical field of environmental monitoring, in particular to a uniform and rapid miniaturized chromatographic device, an atmospheric organic matter measuring system and a measuring method.
Background
The organic matters in the environment atmosphere have wide sources, complex components and wide distribution range, are important precursors of PM2.5 and ozone, and have stronger biological toxicity and directly harm the health of people. The atmospheric organic emission composition is complex, and different organic species play different roles in atmospheric chemical reactions. In order to fully understand the effects of organic matter on the atmosphere and potentially health, it is desirable to accurately determine the composition changes in addition to monitoring the total or partial emissions of atmospheric organic matter. The concentration gradient of the organic matters in the atmosphere is large and the change along with the weather factors is quick, so that new challenges are presented on how to realize the rapid monitoring of the organic matters of multiple species while ensuring the accuracy, the quality and the quantification of the organic matters.
The conventional monitoring technology for organic matters in the ambient air is generally a method of combining gas chromatography or gas chromatography-mass spectrometry with a preconcentrator, the chromatographic analysis period is 30-60 min, and the defects of large volume, low temperature rising speed and the like exist in furnace box heating. At present, more portable heating method technologies are developed and applied to the rapid chromatographic equipment, the heating mode manufacturing process is complex, the operation is troublesome, the implementation is difficult, the device is unstable, and the instrument is easy to damage after multiple uses. In addition, the prior art adopts a resistance type heating mode, the heating rate is low, and the heating is very easy to be uneven. The chromatographic column cooling device has the advantages that the separation capacity of rapid chromatographic temperature rise is limited, in addition, a thicker heat preservation layer is required to be wrapped on the outer surface to ensure certain high temperature, so that a refrigerating device with larger power or larger volume is required to be used for heat dissipation in the chromatographic column cooling stage, the use power and the cost of the device are increased, and the volume of the device is enlarged, so that the device is inconvenient to carry.
Most of the current ion sources are one ion source or a composite of two ion sources, ionized substances are limited, and interference among different ionization sources cannot be avoided structurally. The method can not realize the simultaneous and rapid detection and identification of the atmospheric substances, and generally, a plurality of measuring devices are required to operate simultaneously to realize the measurement and rapid and precise identification of the multiple substances.
Disclosure of Invention
Aiming at the defects of the prior art, the method is optimized in the aspect of analytical chromatographic heating equipment in order to realize the portability requirement of rapid and accurate analysis of atmospheric pollutants. Different from the past regard as the chromatographic column as the change object, this application adopts the metal drum that has magnetic conductivity as heating medium, only need with the chromatographic column evenly tiling twine on the metal drum surface can, perhaps use metal capillary chromatographic column, utilize electromagnetic heating to make metal drum or metal capillary chromatographic column self generate heat to realize the even quick intensification of chromatographic column. The adopted high-power electromagnetic heating has the heating rate of 30 ℃/s, can meet the requirement of rapid heating, does not need to wrap a chromatographic column by a heat preservation layer, and is not only convenient for the heat dissipation of the chromatographic column, but also can check the state of the chromatographic column in real time. The device is placed on a stainless steel plate with a hollowed-out center, and a cooling fan is placed behind the hollowed-out stainless steel plate for cooling the chromatographic column. Finally, a miniaturized micro chromatographic device which is heated uniformly, heated rapidly and warmed up, and has simple operation and low energy consumption is formed.
Because the diversity of analysis sample and the difference of analysis requirement, in order to satisfy diversified analysis requirement, a device realizes the measurement analysis of different substances, and this application has designed trinity's multiple ion source, and EI source ionization efficiency is high, and the energy dispersion is little, simple structure, convenient operation, and the mass spectrogram of obtaining has certain characteristics. Soft ionization sources readily obtain excimer ions that are indicative of relative molecular mass, but have fewer fragment ions that provide structural information, limited ionization capability, and no standard spectral library. To extend ionization capability, EI is integrated with a soft ionization source that is expandable, including H 3 O + 、NH 4 + 、Cl - 、I - And the like, and can be specifically selected according to the nature of the species to be detected. The soft ionization source and the hard ionization source are completely separated through the isolation voltage polar plate, the ionization modes are mutually independent, and a proper ion source is selected for experiments according to the properties of substances and the ionization principle thereof. The selectivity is strong, and various substances are measured in a broad spectrum.
The application provides a miniaturized chromatographic device, an atmospheric organic and/or inorganic substance measuring system and a measuring method.
The technical scheme of the application is as follows:
1. a miniaturized chromatographic device comprises a chromatographic column and a synchronous heating device,
the synchronous heating device directly or indirectly heats the chromatographic column in a non-contact mode, and the chromatographic column is a metal capillary column or a quartz capillary column.
2. The apparatus according to item 1, wherein,
the chromatographic column is a quartz capillary column, the synchronous heating device indirectly heats the chromatographic column,
the miniaturized chromatographic device further comprises a metal cylinder, the chromatographic column is wound outside the metal cylinder in a contact manner, and the synchronous heating device can enable the metal cylinder to generate heat to heat the chromatographic column.
3. The apparatus according to item 1, wherein,
The chromatographic column is a metal capillary column, the synchronous heating device directly heats the chromatographic column, and the synchronous heating device can enable the chromatographic column to heat itself so as to heat the chromatographic column.
4. The apparatus according to item 1, wherein,
the synchronous heating device can heat the chromatographic column to 30-500 ℃;
preferably, the synchronous heating device can enable the temperature rising rate of the chromatographic column to be 2-60 ℃/min, and the synchronous heating device can enable the temperature control precision of the chromatographic column to be +/-0.1 ℃.
5. The apparatus according to item 1, wherein,
the synchronous heating device comprises an electromagnetic heating control board and an induction coil, wherein the electromagnetic heating control board is connected with the induction coil, and the induction coil is arranged at the periphery of the chromatographic column in a non-contact mode so as to heat the chromatographic column.
6. The apparatus according to item 1, wherein,
the inner diameter of the quartz capillary column is 0.1 mm-0.6 mm, preferably any one of 0.53mm, 0.32mm, 0.25mm, 0.18mm and 0.1 mm;
the length of the quartz capillary column is 1 m-30 m; preferably any one of 2.5m, 5m, 10m and 15 m;
the quartz capillary column is selected from one or more of strong polar column, medium polar column, weak polar column and nonpolar column.
7. The apparatus according to item 1, wherein,
the inner diameter of the metal capillary column is 0.1 mm-0.6 mm, preferably any one of 0.2mm, 0.25mm, 0.32mm and 0.53mm,
the length of the metal capillary column is 1 m-30 m,
the metal capillary column is selected from one or more of strong polar column, medium polar column, weak polar column and nonpolar column.
8. The apparatus according to item 2, wherein,
the metal cylinder is hollow, and the material of the metal cylinder is one or more than two of tungsten, molybdenum, ferrosilicon alloy, ferronickel alloy and stainless steel.
9. The apparatus according to item 2 or 3, wherein,
the miniaturized chromatographic device further comprises a temperature sensor, wherein the temperature sensor is arranged between the metal cylinder and the chromatographic column and is used for displaying the temperature of the chromatographic column;
or,
the temperature sensor is arranged at the periphery of the chromatographic column and used for displaying the temperature of the chromatographic column.
10. The apparatus according to item 1, wherein,
the miniaturized chromatographic device further comprises a hollowed-out shell body, wherein the hollowed-out shell body is used for covering the metal cylinder and the chromatographic column or is used for covering the chromatographic column.
11. The apparatus according to item 1, wherein,
The miniaturized chromatography device further comprises a heat dissipation unit; the heat dissipation unit is positioned at the bottom of the hollowed-out shell;
preferably, the heat dissipation unit is a fan.
12. The apparatus according to item 3, wherein,
the volume of the miniaturized chromatographic device is 5cm 20cm 10cm 5cm 20 cm.
13. An atmospheric organic and/or inorganic matter measuring system comprising
The atmospheric organic pretreatment device is divided into an atmospheric organic pretreatment device for EI ionization and an atmospheric organic pretreatment device for charge/proton ionization;
the miniaturized chromatography device according to any one of claims 1-12, connected to an atmospheric organics pretreatment device for EI ionization and/or connected to an atmospheric organics pretreatment device for charge/proton ionization;
the ionization device is divided into an EI ionization device and a charge/proton ionization device, wherein the atmospheric organic matters treated by the miniaturized chromatographic device are connected with the inlet of the EI ionization device, and preferably, the atmospheric organic matters treated by the miniaturized chromatographic device are connected with the inlet of the charge/proton ionization device;
and the detection device is connected with the ionization device and is used for detecting the atmospheric organic matters ionized by EI and the atmospheric organic matters ionized by charge/protons.
14. The measurement system of item 13, wherein,
the outlet of the EI ionization device is provided with a pair of isolation plates for controlling the entry and exit of the atmospheric organic matters ionized by the EI, each isolation plate is provided with a driving slide block, and the driving slide blocks are used for controlling the separation and the closing of the pair of isolation plates;
when the driving sliding block controls the pair of isolation plates to be separated, the atmospheric organic matters ionized by EI can enter the detection device for finely detecting the isomer matters;
when the driving sliding block controls the pair of isolation plates to be closed, the atmospheric organic matters ionized by EI can not enter the detection device, and the atmospheric organic matters ionized by charge/protons can enter the detection device for rapidly detecting the atmospheric organic matters and/or inorganic matters.
15. The measurement system of item 13, wherein,
the atmospheric organic pretreatment device for EI ionization is used for sampling and purging, wherein the sampling is used for sampling atmospheric organic, and the purging is used for removing impurities in a pipeline;
the atmospheric organic pretreatment device for EI ionization sequentially comprises an atmospheric organic sample inlet and outlet pipeline, a three-way valve, a enrichment pipe, a four-way valve and a pump.
16. The measurement system of item 13, wherein,
The atmospheric organic matter pretreatment device for EI ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector;
the atmospheric organic pretreatment device for charge/proton ionization is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector.
17. The measurement system of item 13, wherein,
the atmospheric organic matter pretreatment device for EI ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector;
the atmospheric organic matter pretreatment device for charge/proton ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector.
18. The measurement method using the measurement system according to any one of claims 13 to 17, wherein:
sampling: introducing the atmospheric organics for EI ionization into an atmospheric organics pretreatment device for EI ionization; or, introducing the atmospheric organics for charge/proton ionization into an atmospheric organics pretreatment device for charge/proton ionization;
And (3) a purging step: purging an atmospheric organic pretreatment device for EI ionization and a transmission flow path;
and (3) sample injection: carrying the atmospheric organics treated by the atmospheric organics pretreatment device for EI ionization into a miniaturized chromatographic device and an EI ionization device; or, the atmospheric organic matter treated by the atmospheric organic matter pretreatment device for charge/proton ionization is brought into the miniaturized chromatographic device and the charge/proton ionization device;
the detection step comprises: separating and measuring the atmospheric organic matters subjected to EI ionization treatment; or, separating and measuring the atmospheric organic matters subjected to charge/proton ionization treatment;
or,
sampling: introducing the atmospheric organics for EI ionization into an atmospheric organics pretreatment device for EI ionization; or, introducing the atmospheric organics for charge/proton ionization into an atmospheric organics pretreatment device for charge/proton ionization;
and (3) a purging step: purging an atmospheric organic pretreatment device for EI ionization and a transmission flow path;
and (3) sample injection: carrying the atmospheric organics treated by the atmospheric organics pretreatment device for EI ionization into a miniaturized chromatographic device and an EI ionization device; or, carrying the atmospheric organic matters treated by the atmospheric organic matter pretreatment device for charge/proton ionization into the charge/proton ionization device;
The detection step comprises: separating and measuring the atmospheric organic matters subjected to EI ionization treatment; or, the atmospheric organic matter subjected to charge/proton ionization treatment is separated and measured.
Compared with the prior art, the beneficial effects of this application are:
the application uses the current chemical component diversity monitoring and accurate measurement of environmental atmospheric substances as research purposes, develops a miniaturized chromatographic device capable of realizing uniform heating and quick separation of substances, is integrated with a multiple ion source mass spectrum detector, can form an atmospheric substance direct, fine and compound online measurement system which is mutually complementary, can pointedly carry out quick separation and identification on the atmospheric substances while meeting the quick measurement, and provides technical support for accurate tracing and management and control of the atmosphere.
At present, the existing rapid monitoring mode using single direct sample injection-mass spectrometry measurement as the atmospheric pollutants cannot realize the separation and identification of isomers by the measurement principle. However, the atmospheric components are more complex, the isomers are more abundant, and substances with the same molecular weight represent different physicochemical characteristics, so that the isomers need to be identified in order to realize accurate measurement and tracing of the atmospheric pollutants. Therefore, the miniaturized GC system is used together with the mass spectrum detector, so that the method and the technology can realize the rapid measurement of substances and effectively identify various homoheavy compounds;
The application uses a cylindrical metal cylinder as a heating and heat transfer medium, and only needs to directly wind the chromatographic column made of quartz material onto the metal cylinder, adopts an electromagnetic heating technology, so that the cylindrical metal cylinder generates heat by itself, and the heat is directly conducted to the chromatographic column. Or, the metal chromatographic column is used as a heating medium, and an electromagnetic heating technology is adopted, so that the metal chromatographic column generates heat. The design of the application can ensure the uniform temperature rise of the chromatographic column, does not need complex chromatographic column pretreatment flow, and is simple to operate; in addition, in view of the rapid heating rate (30 ℃/s) of electromagnetic heating, an insulating layer does not need to be wrapped on the outer surface, the requirement of chromatograph on rapid heat dissipation and cooling can be met by using a simple fan, the working efficiency of the device is improved, the volume of equipment is reduced, and the device is convenient to carry.
In order to furthest meet ionization measurement of different atmospheric samples, the multi-ion source system is developed, soft ionization can select proton transfer taking water as a reagent molecule or charge transfer ionization reaction taking oxygen as a reagent gas, the ion source has the advantages of charge transfer, proton transfer and EI, three positions are integrated into a whole, universality is strong, and different analysis samples can be analyzed by selecting proper ionization sources. In order to reduce the interference between different ion sources to the maximum extent, a slidable isolation polar plate is arranged, and the opening and closing of the polar plate are controlled by a driving device, so that different ion sources are isolated, the ionization sources can independently operate, and the detection accuracy is improved.
In order to expand the application of simultaneous monitoring of multiple pollutants, the miniature chromatographic device and the multiple ion source mass spectrum are integrated, the direct, fine and composite multiple sample injection measurement mode selection can be realized, the direct measurement mode of only soft ionization or the chromatographic separation measurement mode can be selected according to the measurement requirement, the different modes can be compositely applied, namely, the chromatographic separation fine measurement can be carried out according to the measurement requirement of the rapid separation mixed components after the primary investigation of the atmospheric environment, the two modes are mutually complemented, and the multifunctional selection is provided for the measurement of atmospheric substances.
The developed miniaturized chromatographic device is applied to an atmospheric organic matter detection system, can be integrated with EI source mass spectrum, and can be used for measuring the concentration information of the atmospheric organic matters. In order to expand the practicability of the instrument, the proton transfer source and the CI source are integrated into a multiple ionization source, so that the change information of substances can be captured in real time through non-chromatographic separation soft ionization mass spectrometry, and finer substance information can be obtained through a rapid separation chromatographic-EI source mass spectrometry detection system, so that the types of substances from atmospheric pollution can be accurately identified, and technical support is provided for scientific management and control.
The full spectrum information of the atmospheric pollutants is firstly obtained through a rapid direct sample injection soft ionization mass spectrometry technology, the approximate pollution types are screened out, and then refined separation detection is carried out on the pollution types according to GC-EI, so that the specific pollutant composition and concentration level are identified, and the real high-concentration pollutants are accurately locked. In addition, in order to meet the ionization measurement of different atmospheric samples to the maximum extent, a multiple ion source system is developed, soft ionization can select proton transfer with water as a reagent molecule or charge transfer reaction with oxygen as a reagent gas, the ion source has the advantages of charge transfer, proton transfer and EI, and a proper reagent can be selected as CI for different analysis samples - Is a reaction reagent ion of (a).
Drawings
FIGS. 1A and 1B show schematic diagrams of a chromatographic column of the present application;
FIG. 2 shows a schematic diagram of a miniaturized chromatography device of the present application;
FIG. 3 shows a schematic diagram of a miniaturized chromatography device of the present application in connection with an ionization device;
FIG. 4 illustrates an atmospheric organics and/or inorganics measurement system of the present application;
FIG. 5 illustrates an atmospheric organics and/or inorganics measurement system of the present application;
FIG. 6 shows graphs of the results of the measurement standard nC10-C25 normal alkane samples of the present application;
FIG. 7 shows a graph of the results of the present application for measuring atmospheric organics;
FIG. 8 shows a graph of the results of the standard 6 polycyclic aromatic hydrocarbons and standard nC10-C35 normal alkane aerosol samples of the present application;
fig. 9 shows a schematic of the results of comparative example 1 of the present application.
1. Temperature sensor, 2 chromatographic column, 2A quartz chromatographic column, 2B metal chromatographic column, 3 metal column, 4 induction coil, 5 hollowed-out housing, 6 fan, 7 three-way valve, 8 manifold, 9 four-way valve, 10 flow controller, 11 sampling pump, 12 miniaturized chromatography unit, 13 electromagnetic heating control board, 14 multiple ion source mass spectrum, 15 gas supply and pressure control system, 16 computer interaction control system, 17 driving slide block, 18 isolation board, 19 EI ionization device, 20 switching valve, 21 reagent bottle, 22 standard gas bottle, 23 ionization zone, 24 lens group, 25 mass analysis component, 26 detector, 27 two-way valve, 28 second three-way valve, 29 shunt valve (29), 30 high temperature fixing band.
Detailed Description
The present application is further illustrated below with reference to examples, it being understood that the examples are for further illustration and explanation of the application only and are not intended to limit the application.
Unless defined otherwise, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the materials and methods are described herein below. In case of conflict, the present specification, including definitions therein, will control and materials, methods, and examples, will control and be in no way limiting. The present application is further illustrated below in conjunction with specific examples, but is not intended to limit the scope of the present application.
In the prior art, in the process of soft ionization source reagent ion switching, a voltage reversal method is basically adopted for rapid switching, although the switching speed is very high in theory, different ion sources can share a common interval, and residual ions of the different ion sources, reagent neutral molecules and other interfering substances cannot be rapidly discharged, so that the purity and detection sensitivity of the different ion sources can be greatly interfered. The simple use of voltage switching does not eliminate neutral reagent molecules and has limited removal of other interfering ions.
In order to reduce interference among different ion sources, the application adopts the isolation plate to isolate the different ion sources in the geographic position under the premise of voltage switching control, so that cross mixing among ions is reduced. In addition, reagent gas is adopted to rapidly pre-flush the ion source and the transmission pipeline when the ion source is switched, and the residual ions in the ion source area, neutral molecules and other interference substances are rapidly discharged, so that the interference to effective ions of the next ion source is reduced, the measurement sensitivity is increased, and the accuracy is improved.
In the present application, charge ionization refers to chemical ionization based on charge transfer reactions, reagent gas ions (more commonly NO + And O 2 + Ion) and the molecules of the substance to be detected are subjected to ionic molecular reaction through charge exchange, so that the substance to be detected is ionized.
In the present application, proton ionization refers to chemical ionization based on proton transfer reactions, reagent gas ions (H 3 O + ) Ion molecular reaction is carried out on the ion exchange reaction product and the substance to be detected through proton exchange, so that the substance to be detected is ionized.
By H 3 O + The ionization mode of the parent ion needs that the proton affinity of the substance to be detected is higher than that of water and can not be ionized, and the proton ionization source can not realize the effective ionization of compounds such as low-carbon alkane, olefin below C3, short-chain chlorinated hydrocarbon, carbon disulfide and the like due to the limitation of the proton affinity. But can be modified by changing the parent ion mode using charge ionization (O 2 + ) Mode realization of proton transferComplement to the ionization mode. The detection range of the instrument is expanded by the multiple species of parent ions, and some substances with proton affinity less than that of water can be detected. Some molecules to be detected can obtain different product ions when reacting with different parent ions, so that the qualitative capability of the target object is relatively improved. In this application, EI ionization refers to the electron bombardment source, which is the earliest and most widely used ionization mode. The filament of the EI source emits electrons with 70eV collision energy that ionize the molecules to be measured and further break down to produce abundant fragment ions.
The charge/proton ionization front end has no column separation, so that the isomers are not subjected to differential analysis, the total amount of the corresponding isomers is generally given, and the qualitative ability of unknown substances is limited because of the absence of a standard spectrum library. The commonly used NIST standard spectrum library is a standard spectrum library established by the national institute of technology according to EI sources, and is relatively easy to characterize for unknown substances and isomers.
In the present application, charge/proton ionization refers to an ionization source that integrates charge ionization with proton ionization, and the generation and switching of reagent ions can be controlled to alternately use charge ionization or proton ionization to ionize a substance to be measured.
The application provides a miniaturized chromatographic device, wherein, including chromatographic column and synchronous heating device, synchronous heating device is with non-contact mode directly or indirectly right the chromatographic column heats, the chromatographic column is metal capillary column or quartz capillary column.
As shown in fig. 1A, the chromatographic column is a quartz capillary column (2A), the synchronous heating device indirectly heats the chromatographic column, the miniaturized chromatographic device further comprises a metal cylinder (3), the chromatographic column (2) is wound outside the metal cylinder (3) in a contact manner, and the synchronous heating device (4) can enable the metal cylinder (3) to generate heat by itself so as to heat the chromatographic column (2A).
As shown in fig. 1B, the chromatographic column is a metal capillary column (2B), and the synchronous heating device directly heats the chromatographic column, and the synchronous heating device can enable the chromatographic column to generate heat by itself so as to heat the chromatographic column. Wherein, the periphery of the chromatographic column is also provided with a high-temperature fixing belt (30) for fixing the metal chromatographic column, preventing the metal chromatographic column from loosening and uniformly sensing the electromagnetic effect to heat.
The heating mode of this application has improved the heating mode under the portable prerequisite of assurance chromatographic device miniaturization, adopts the electromagnetic synchronous heating mode that consumes less power, long service life, intensification are fast, has solved the inhomogeneous problem of chromatographic column temperature that the resistance heating that miniature chromatograph used in the present market led to. The device is simple in arrangement, utilizes electromagnetic heating to heat at a high speed, and utilizes the metal cylinder/metal chromatographic column to synchronously and directly/indirectly heat, so that the uniform heating of the chromatographic column is realized. Can be applied to different chromatographic devices.
In some embodiments of the present application, the synchronous heating device (4) may heat the chromatographic column to 30-500 ℃; for example, the simultaneous heating device (4) may heat the column to 30 ℃, 50 ℃, 75 ℃, 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃, 300 ℃, 325 ℃, 350 ℃, 375 ℃, 400 ℃, 425 ℃, 450 ℃, 475 ℃, 500 ℃ or any range therebetween.
In some embodiments of the present application, the synchronized heating means (4) enables a temperature rise rate of the chromatography column of 2-60 ℃/min, e.g., the synchronized heating means (4) enables a temperature rise rate of the chromatography column of 2 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, 25 ℃/min, 30 ℃/min, 35 ℃/min, 40 ℃/min, 45 ℃/min, 50 ℃/min, or any range therebetween.
In some embodiments of the present application, the synchronous heating device enables temperature control accuracy of the chromatographic column to be + -0.1 ℃.
In some embodiments of the present application, the synchronous heating device (4) comprises an electromagnetic heating control board (13) and an induction coil (4), wherein the electromagnetic heating control board (13) is connected with the induction coil (4), and the induction coil (4) is arranged at the periphery of the chromatographic column (2) in a non-contact manner so as to heat the chromatographic column.
As shown in fig. 1A, the metal cylinder (3) is hollow, and the metal cylinder (3) is made of one or more materials selected from tungsten, molybdenum, ferrosilicon, ferronickel and stainless steel. The hollow metal cylinder can be used as a supporting piece, a heating and heat transferring unit for heating the quartz capillary column, and a fixing device of a heat radiating unit.
In some embodiments of the present application, the quartz capillary column has an inner diameter of 0.1mm to 0.6mm.
In some embodiments of the present application, the quartz capillary column has an inner diameter of any one of 0.53mm, 0.32mm, 0.25mm, 0.18mm, 0.1 mm.
In some embodiments of the present application, the length of the quartz capillary column is from 1m to 30m.
In some embodiments of the present application, the length of the quartz capillary column is any of 2.5m, 5m, 10m, 15 m.
In some embodiments of the present application, the quartz capillary column is selected from one or more of a strong polarity column, a medium polarity column, a weak polarity column, a non-polar column.
In the present application, the inner diameter, length and polarity of the quartz capillary column are not limited, and those skilled in the art can select a suitable inner diameter, length and polarity according to actual needs.
In some embodiments of the present application, the inner diameter of the metallic capillary column is 0.1mm to 0.6mm.
In some embodiments of the present application, the inner diameter of the metal capillary column is any one of 0.2mm, 0.25mm, 0.32mm, and 0.53 mm.
In some embodiments of the present application, the length of the metallic capillary column is from 1m to 30m. In some embodiments of the present application, the metal capillary column is selected from one or more of a strong polarity column, a medium polarity column, a weak polarity column, a non-polar column.
In the present application, the inner diameter, length and polarity of the metal capillary column are not limited, and those skilled in the art can select an appropriate inner diameter, length and polarity according to actual needs.
As shown in fig. 1A, the miniaturized chromatographic apparatus further comprises a temperature sensor (1), wherein the temperature sensor (1) is arranged between the metal cylinder (3) and the quartz chromatographic column (2A) and is used for displaying the temperature of the chromatographic column;
as shown in fig. 1B, the miniaturized chromatographic apparatus further includes a temperature sensor (1), where the temperature sensor (1) is disposed at the periphery of the chromatographic column (2B) and is used for displaying the temperature of the chromatographic column.
As shown in fig. 2, the miniaturized chromatography device further comprises a hollowed-out casing (5) for covering the metal cylinder (3) and the chromatography column (2) or for covering the chromatography column (2).
As shown in fig. 2, the miniaturized chromatography device further comprises a heat dissipation unit (6); the heat dissipation unit (6) is positioned at the bottom of the hollowed-out shell (5).
In some embodiments of the present application, the heat dissipating unit (6) is a fan.
In some embodiments of the present application, the miniaturized chromatography device has a volume of 5cm x 5cm to 20cm x 10cm. For example, the number of the cells to be processed, 5cm, 10cm 5cm, 15cm 5cm, 20cm 5cm, 5cm 10cm 5cm, 10cm 5cm, 15cm 10cm 5cm, 20cm 5cm, 15cm 5cm, 20cm 5cm, 5cm 10cm x 15cm x 5cm, 15cm x 5cm, 20cm x 15cm x 5cm, 5cm x 20cm x 5cm, 10cm x 20cm x 5cm, 15cm x 20cm x 5cm, 5cm x 10cm, 10cm x 5cm x 10cm 15cm x 5cm x 10cm, 20cm x 5cm x 10cm, 10cm x 10cm, 15cm x 10cm, 20cm x 10cm, 5cm x 15cm x 10cm, 10cm x 15cm x 10cm, 15cm x 15cm, 20cm x 10cm, 20cm x 15cm, 5cm x 20cm x 10cm, 10cm x 20cm, 15cm x 20cm x 10cm, or any range therebetween.
The application provides an atmospheric organic and/or inorganic substance measuring system, which comprises an atmospheric organic substance pretreatment device, an atmospheric organic substance pretreatment device for EI ionization and an atmospheric organic substance pretreatment device for charge/proton ionization, wherein the atmospheric organic substance pretreatment device is used for carrying out EI ionization; the miniaturized chromatography device is connected with an atmospheric organic pretreatment device for EI ionization and/or connected with an atmospheric organic pretreatment device for charge/proton ionization; the ionization device is divided into an EI ionization device and a charge/proton ionization device, wherein the atmospheric organic matters treated by the miniaturized chromatographic device are connected with the inlet of the EI ionization device, and preferably, the atmospheric organic matters treated by the miniaturized chromatographic device are connected with the inlet of the charge/proton ionization device; and the detection device is connected with the ionization device and is used for detecting the atmospheric organic matters ionized by EI and the atmospheric organic matters ionized by charge/protons.
According to the atmospheric organic and/or inorganic substance measuring system, conventional gas-phase organic substances such as C2-C12 volatile organic substances and C13-C24 semi-volatile organic substances can be detected, C7-C40 aerosol substances can be measured, and a heat tracing device is arranged on a sample injection pipeline, so that the aerosol substances can be directly measured by heating the aerosol substances to 300 ℃. The electric voltage of proton transfer can also be reversed, and the reagent water is directly ionized into OH - Ions, which can measure NO 2 、CO 2 、SO 2 The inorganic matters provide technical support for the research of the gas phase production path of the atmospheric nitrate.
As shown in fig. 3, the outlet of the EI ionization device (19) is provided with a pair of isolation plates (18) for controlling the ingress and egress of atmospheric organic matter ionized by the EI, each isolation plate (18) is provided with a driving slide block (17), and the driving slide block (17) is used for controlling the separation and closure of the pair of isolation plates (18).
In the application, when the driving slide block (17) controls the pair of isolation plates (18) to be separated, the EI ionized atmospheric organic matters can enter a detection device for finely detecting the isomer matters; when the driving sliding block (17) controls the pair of isolation plates (18) to be closed, the atmospheric organic matters ionized by EI can not enter the detection device, and the atmospheric organic matters ionized by charge/protons can enter the detection device for rapidly detecting the atmospheric organic matters and/or inorganic matters.
As shown in fig. 3, the atmospheric organics pretreatment device for EI ionization is used for sampling atmospheric organics and purging for removing impurities in the pipeline. The impurities are mainly oxygen, which has destructive effect on the heated chromatographic column and also removes N 2 、CO 2 These areAnd (3) not surplus substances to be detected.
The atmospheric organic pretreatment device for EI ionization sequentially comprises an atmospheric organic sample inlet and outlet pipeline, a three-way valve (7), an enrichment pipe (8), a four-way valve (9) and a sampling pump (11); after sampling is completed, the carrier gas is required to be used for purging non-detection substances in the pipeline, so that the loss of substances such as oxygen and the like to the chromatographic column is avoided, and the three-way valve (7), the enrichment pipe (8), the four-way valve (9) and the sampling pump (11) are used in the purging step. The flow controller (10) is used for realizing accurate control of the atmosphere sampling volume.
As shown in fig. 4, the charge/proton ionization device comprises a switching valve (20), a reagent bottle (21), a gas target bottle (22), an ionization region (23) and a lens group (24), different reagent ions can be selected according to the requirement to carry out selective ionization detection on the substance to be detected, when using H 3 O + When ionization of the substance to be detected is carried out, the public end of the control switching valve (20) is communicated with the reagent bottle (21), the reagent bottle (21) is heated, and water vapor enters the ionization region (23) through the switching valve (20) and the reagent sample injection pipeline to be ionized into H 3 O + Ion molecular reaction is carried out on the ion molecular reaction product and the substance to be detected in the subsequent reaction zone, and the ion molecular reaction product enters a subsequent detection system after being subjected to shaping and focusing through a lens group (24); when O is used 2 + Or NO + When ionization measurement is carried out on a substance to be detected, the public end of the switching valve (20) is controlled to be communicated with the gas standard bottle (22), and reagent gas enters the ionization region (23) through the switching valve (20) and the reagent sample injection pipeline to be ionized into O 2 + Or NO + Ion molecular reaction is carried out on the ion molecular reaction product and the substance to be detected in the subsequent reaction zone, and the ion molecular reaction product enters a subsequent detection system after being subjected to shaping and focusing through a lens group (24);
as shown in fig. 4, the atmospheric organic pretreatment device for the ionization of EI is connected with the miniaturized chromatography device (12), the atmospheric organic treated by the miniaturized chromatography device is connected with the inlet of the EI ionization device (19), and the EI ionization device is connected with the detector (26); the atmospheric organic pretreatment device for charge/proton ionization is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector. At the moment, the method can be used for rapidly determining the quality, and the detection modes such as GC and EI have standard NIST spectrum libraries, so that the identification substances can be directly compared, and the method is rapid, accurate and convenient; charge/proton soft ionization can also be coupled to GC.
As shown in fig. 5, the atmospheric organic pretreatment device for the ionization of EI is connected with the miniaturized chromatography device (12), the atmospheric organic treated by the miniaturized chromatography device is connected with the inlet of the EI ionization device (19), and the EI ionization device is connected with the detector; the atmospheric organic pretreatment device for charge/proton ionization is connected with the miniaturized chromatography device (12), the atmospheric organic treated by the miniaturized chromatography device is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector (26). At this time, the rapid qualitative and quantitative interaction can be realized, most of the ionization of substances by charge/proton soft ionization is molecular ion peak, but isomers cannot be identified, most of the substances can be rapidly qualitative and quantitative after being combined with GC, but some substances with low proton affinity are ionized out of molecular ion peak, the mass spectrogram is not easy to identify, the detection modes of GC and EI can be sampled, and standard NIST spectrum library is utilized for identification. The mode of combining the two can ensure the effective identification of the atmospheric organic matters, and avoids the phenomenon of mutual interference of overlapping peaks.
The application provides a measurement method of the measurement system, which comprises the following steps:
sampling: introducing the atmospheric organics for EI ionization into an atmospheric organics pretreatment device for EI ionization; or, introducing the atmospheric organics for charge/proton ionization into an atmospheric organics pretreatment device for charge/proton ionization;
and (3) a purging step: purging an atmospheric organic pretreatment device for EI ionization and a transmission flow path;
and (3) sample injection: carrying the atmospheric organics treated by the atmospheric organics pretreatment device for EI ionization into a miniaturized chromatographic device and an EI ionization device; or, the atmospheric organic matter treated by the atmospheric organic matter pretreatment device for charge/proton ionization is brought into the miniaturized chromatographic device and the charge/proton ionization device;
the detection step comprises: separating and measuring the atmospheric organic matters subjected to EI ionization treatment; or, separating and measuring the atmospheric organic matters subjected to charge/proton ionization treatment;
or,
sampling: introducing the atmospheric organics for EI ionization into an atmospheric organics pretreatment device for EI ionization; or, introducing the atmospheric organics for charge/proton ionization into an atmospheric organics pretreatment device for charge/proton ionization;
And (3) a purging step: purging an atmospheric organic pretreatment device for EI ionization and a transmission flow path;
and (3) sample injection: carrying the atmospheric organics treated by the atmospheric organics pretreatment device for EI ionization into a miniaturized chromatographic device and an EI ionization device; or, carrying the atmospheric organic matters treated by the atmospheric organic matter pretreatment device for charge/proton ionization into the charge/proton ionization device;
the detection step comprises: separating and measuring the atmospheric organic matters subjected to EI ionization treatment; or, the atmospheric organic matter subjected to charge/proton ionization treatment is separated and measured.
As shown in fig. 4, the pretreatment device of the atmospheric organic matters for the ionization of the EI is connected with the miniaturized chromatography device, the atmospheric organic matters treated by the miniaturized chromatography device are connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector; the atmospheric organic pretreatment device for charge/proton ionization is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector. The device is convenient for quick qualitative, and the detection modes such as GC and EI have standard NIST spectrum libraries, so that the comparison of which identification substance is can be directly carried out, and the result is quick, accurate and convenient;
As shown in fig. 4, at this time, the detection method is as follows: the specific implementation method comprises the following steps:
the system can realize accurate and rapid identification of atmospheric multi-component organic matters, lock specific information of high-concentration organic matters and provide data support for pollution sources and accurate tracing through a direct sample injection/EI sampling mode, a direct sample injection/purging mode, a switching mode, a GC rapid separation-measurement mode and a cooling standby mode.
The method specifically comprises the following steps:
direct sample injection/EI sampling mode: the computer interaction control system (16) controls the enrichment pipe (8) to be in a low-temperature collection state, and atmospheric samples are captured into the enrichment pipe (8) after passing through the electric three-way valve (7) under the suction action of the sampling pump (11) (wherein the inside of the enrichment pipe (8) can be added with an adsorbent or can be empty pipe), and the enrichment time is determined according to actual atmospheric samples. At this time, the miniaturized chromatographic device (12) is in a standby state, the chromatographic column fan (6) is started, and carrier gas is blown into the miniaturized chromatographic device (12) through the four-way valve (9) after coming out of the gas supply and gas path pressure control system (15) to protect the carrier gas of the chromatograph; EI is in an isolated state, and the driving slide block (17) is controlled to be in a closed state, so that the EI area is completely isolated from the soft ionization area, and mutual interference is reduced. The other atmosphere sample directly enters the reaction area of the CI source through the suction force of the mass spectrum, the two-way valve (27) is controlled to be in an open state, different reagents are selected to enter the reagent ionization area according to sample information, generated reagent ions enter the subsequent reaction area and are subjected to charge exchange or proton exchange plasma reaction with atmosphere sample molecules, generated ions of the species to be detected are subjected to subsequent focusing of the lens group (24) and quantitative detection by the detector (26) after the mass analysis component (25).
Direct injection/EI purge mode: after the sampling is finished, the computer interaction control system (16) controls the enrichment pipe (8) to be still in a low-temperature acquisition state, and the carrier gas is discharged through the sampling pump (11) after passing through the electric three-way valve (7) and the enrichment pipe (8), so that oxygen and the like in the enrichment pipe (8) are purged and removed. At this time, the miniaturized chromatographic device (12) is in a standby state, the chromatographic column fan (6) is started, and carrier gas is blown into the miniaturized chromatographic device (12) through the four-way valve (9) after coming out of the gas supply and gas path pressure control system (15) to protect the carrier gas of the chromatograph; at this time, the soft ionization measurement mode is in the direct sample injection detection stage.
Switching modes: the soft ionization detection mode is faster in time, analysis is carried out according to measured substance information, a mass number range needing fine detection is selected, and a corresponding chromatographic column temperature programming method is designed for the mass number. In the switching mode, the isolation plate (18) is pulled open by the driving slide block (17) to leave a gas path channel, at the moment, the switching valve (20) is in a closed state, no reagent gas enters the ionization source, interference to EI ionization is avoided, and the two-way valve (27) is also in a closed state, so that no sample enters.
EI-GC fast separation-measurement mode: the computer interaction control system (16) controls the enrichment pipe (8) to heat and raise the temperature, the carrier gas brings the organic matters to be detected enriched in the enrichment pipe (8) into the micro chromatographic device (12) for separation through the four-way valve (9) after passing through the electric three-way valve (7), the computer interaction control system (16) controls the electromagnetic controller to quickly raise the temperature of the chromatographic column (2) according to a set temperature programming method, and the separated matters are ionized through the EI ionization device and enter the subsequent modules for quantitative detection.
Cooling standby mode: after one round of measurement is completed, the computer interaction control system (34) controls the enrichment tube (8) and the miniaturized chromatographic device (12) to be in a low-temperature state, the isolation plate (18) is in a closed state, the reagent gas is in an open state, and the next sample injection ionization flow is waited.
Wherein, the EI sampling mode refers to sampling in EI ionization mode;
the EI purge mode refers to purge in the EI ionization mode;
EI-GC rapid separation refers to rapid separation based on EI ionization patterns and in the case of miniaturized chromatographic devices.
As shown in fig. 5, the pretreatment device of the atmospheric organic matters for the ionization of the EI is connected with the miniaturized chromatography device, the atmospheric organic matters treated by the miniaturized chromatography device are connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector; the atmospheric organic matter pretreatment device for charge/proton ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector. The device can realize mutually assisted rapid qualitative and quantitative determination. The charge/proton soft ionization ionizes most of substances as molecular ion peaks, but can not identify isomers, and most of substances can be rapidly and qualitatively quantified after being combined with GC, but the substances with low proton affinity ionize out not as molecular ion peaks, so that the mass spectrogram is not easy to identify, and the detection mode of GC+EI can be sampled and identified by using a standard NIST spectrum library. The mode of combining the two can ensure the effective identification of the atmospheric organic matters, and avoids the phenomenon of mutual interference of overlapping peaks.
As shown in fig. 5, at this time, the detection method is as follows: the specific implementation method comprises the following steps:
the system can realize accurate and rapid identification of atmospheric multicomponent organic matters, lock the specific information of high-concentration organic matters and provide data support for pollution sources and accurate tracing through a direct sample injection/sampling mode, a direct sample injection/purging mode, a switching mode, a GC rapid separation-measurement mode and a cooling standby mode.
The method specifically comprises the following steps:
GC direct sample/EI sampling mode: the computer interaction control system (16) controls the enrichment pipe (8) to be in a low-temperature collection state, and atmospheric samples are captured into the enrichment pipe (8) after passing through the electric three-way valve (7) under the suction action of the sampling pump (11) (wherein the inside of the enrichment pipe 8 can be added with an adsorbent or can be empty pipes), and the enrichment time is determined according to actual atmospheric samples. At the moment, the EI is in an isolated state, the driving slide block (17) is controlled to be in a closed state, and the EI area is completely isolated from the soft ionization area, so that mutual interference is reduced. The other atmospheric sample enters the miniaturized chromatographic device (12) through the second three-way valve (28) by the suction force of the mass spectrum to separate, the isomer in the sample is rapidly separated, the sample directly enters the reaction zone of the CI source through the flow dividing valve (29), the two-way valve (27) is controlled to be in an open state, different reagents are selected according to sample information to enter the reagent ionization zone, the generated reagent ions enter the subsequent reaction zone to carry out charge exchange or proton exchange plasma reaction with atmospheric sample molecules, and the generated ions of the species to be detected are focused by the subsequent lens group (24), and quantitatively detected by the detector (26) after the mass analysis component (25).
GC direct injection/EI purge mode: after the sampling is finished, the computer interaction control system (16) controls the enrichment pipe (8) to be still in a low-temperature acquisition state, and the carrier gas is discharged through the sampling pump (11) after passing through the electric three-way valve (7) and the enrichment pipe (8), so that oxygen and the like in the enrichment pipe (8) are purged and removed. At this time, the GC module, the soft ionization measurement mode, is in the direct sample injection detection stage.
Switching modes: and analyzing according to the measured substance information, selecting the substance information which cannot be directly identified, and designing a corresponding chromatographic column temperature programming method. In the switching mode, the isolation plate (18) is pulled open by the driving slide block (17) to leave a gas path channel, at the moment, the switching valve (20) is in a closed state, no reagent gas enters the ionization source, interference to EI ionization is avoided, and the two-way valve (27) is also in a closed state, so that no sample enters.
EI-GC fast separation-measurement mode: the computer interaction control system (16) controls the enrichment pipe (8) to heat and raise the temperature, the carrier gas brings the organic matters to be detected enriched in the enrichment pipe (8) into the micro chromatographic device (12) for separation through the four-way valve (9) after passing through the electric three-way valve (7), the computer interaction control system (16) controls the electromagnetic controller to quickly raise the temperature of the chromatographic column according to a set temperature programming method, and the separated matters enter the EI ionization device (19) for ionization after passing through the flow dividing valve (29) and enter the subsequent modules for quantitative detection.
Cooling standby mode: after one round of measurement is completed, the computer interaction control system (16) controls the enrichment tube (8) and the miniaturized chromatographic device (12) to be in a low-temperature state, the isolation plate (18) is in a closed state, the reagent gas is in an open state, and the next sample injection ionization flow is waited.
Wherein, GC direct sample injection refers to sample injection based on a miniaturized chromatographic device;
the EI sampling mode refers to sampling based on EI ionization;
the EI purging mode refers to purging based on EI ionization;
EI-GC rapid separation refers to rapid separation based on EI ionization patterns and in the case of miniaturized chromatographic devices.
Examples
Example 1
As shown in fig. 4, the pretreatment device of the atmospheric organic matters for the ionization of the EI is connected with the miniaturized chromatography device, the atmospheric organic matters treated by the miniaturized chromatography device are connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector; the atmospheric organic pretreatment device for charge/proton ionization is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector. The device is convenient for quick qualitative, and the detection modes such as GC and EI have standard NIST spectrum libraries, so that the comparison of which identification substance is can be directly carried out, and the result is quick, accurate and convenient;
The miniaturized chromatographic device is shown in fig. 2, and comprises a metal cylinder (3), a quartz chromatographic column (2A), a synchronous heating device, a temperature sensor (1), a hollowed-out shell (5) and a fan (6), wherein the chromatographic column is a quartz capillary column, the synchronous heating device comprises an electromagnetic heating control board and an induction coil, the inner diameter of the quartz capillary column is 0.53mm, the length of the quartz capillary column is 5m, the quartz capillary column is a medium-polarity column, the metal cylinder is hollow, and the metal cylinder is made of tungsten.
As shown in fig. 4, at this time, the detection method is as follows: the specific implementation method comprises the following steps:
the system can realize accurate and rapid identification of atmospheric multicomponent organic matters, lock the specific information of high-concentration organic matters and provide data support for pollution sources and accurate tracing through a direct sample injection/sampling mode, a direct sample injection/purging mode, a switching mode, a GC rapid separation-measurement mode and a cooling standby mode.
The method specifically comprises the following steps:
direct sample injection/EI sampling mode: the computer interaction control system (16) controls the enrichment pipe (8) to be in a low-temperature collection state, and atmospheric samples are captured into the enrichment pipe (8) after passing through the electric three-way valve (7) under the suction action of the sampling pump (11), and the enrichment time is determined according to actual atmospheric samples. At the moment, the GC module is in a standby state, the chromatographic column fan (6) is started, and carrier gas is blown into the miniaturized chromatographic device (12) through the four-way valve (9) after coming out of the gas supply and gas path pressure control system (15) to carry out carrier gas protection on the chromatograph; EI is in an isolated state, and the driving slide block (17) is controlled to be in a closed state, so that the EI area is completely isolated from the soft ionization area, and mutual interference is reduced. The other atmosphere sample directly enters the reaction area of the CI source through the suction force of the mass spectrum, the two-way valve (27) is controlled to be in an open state, different reagents are selected to enter the reagent ionization area according to sample information, generated reagent ions enter the subsequent reaction area and are subjected to charge exchange or proton exchange plasma reaction with atmosphere sample molecules, generated ions of the species to be detected are subjected to subsequent focusing of the lens group (24) and quantitative detection by the detector (26) after the mass analysis component (25).
Direct injection/EI purge mode: after the sampling is finished, the computer interaction control system (16) controls the enrichment pipe (8) to be still in a low-temperature acquisition state, and the carrier gas is discharged through the sampling pump (11) after passing through the electric three-way valve (7) and the enrichment pipe (8), so that oxygen and the like in the enrichment pipe (8) are purged and removed. At this time, the miniaturized chromatographic device (12) is in a standby state, the chromatographic column fan (6) is started, and carrier gas is blown into the miniaturized chromatographic device (12) through the four-way valve (9) after coming out of the gas supply and gas path pressure control system (15) to protect the carrier gas of the chromatograph; at this time, the soft ionization measurement mode is in the direct sample injection detection stage.
Switching modes: the soft ionization detection mode is faster in time, analysis is carried out according to measured substance information, a mass number range needing fine detection is selected, and a corresponding chromatographic column temperature programming method is designed for the mass number. In the switching mode, the separation plate (18) is pulled open by the driving slide block (17) to leave a gas path channel, at the moment, the switching valve (20) is in a closed state, no reagent gas enters the ionization source, interference to EI ionization is avoided, and the two-way valve (27) is also in a closed state, so that no sample enters.
EI-GC fast separation-measurement mode: the computer interaction control system (16) controls the enrichment pipe (8) to heat and raise the temperature, the carrier gas brings the organic matters to be detected enriched in the enrichment pipe (8) into the micro chromatographic device (12) for separation through the four-way valve (9) after passing through the electric three-way valve (7), the computer interaction control system (16) controls the electromagnetic controller to quickly raise the temperature of the chromatographic column according to a set temperature programming method, and the separated matters are ionized through the EI ionization device (19) and enter the subsequent modules for quantitative detection.
Cooling standby mode: after one round of measurement is completed, the computer interaction control system (16) controls the enrichment tube (8) and the miniaturized chromatographic device (12) to be in a low-temperature state, the isolation plate (18) is in a closed state, the reagent gas is in an open state, and the next sample injection ionization flow is waited.
Wherein a standard nC10-C25 normal alkane sample is measured using the above system and method; as a result, as can be seen from fig. 6, the system and method of the present application can achieve complete detection of normal paraffins in a short period of time.
The system and the method can be used for directly measuring the atmospheric organic matters, and the result is shown in fig. 7, and as can be seen from fig. 7, the system and the method can be used for rapidly screening and detecting the isomers.
In example 1, the charge/proton ionization was integrated, so that the problem that some compounds cannot be effectively ionized due to a specific ionization mechanism, so that detection cannot be performed, and measurement of various substances can be realized.
The results of measuring standard 6 polycyclic aromatic hydrocarbons and standard nC10-C35 normal paraffin aerosol samples using the above system and method are shown in fig. 8, and the individual peaks of the substances can be measured and identified faster.
Example 2
As shown in fig. 5, the pretreatment device of the atmospheric organic matters for the ionization of the EI is connected with the miniaturized chromatography device, the atmospheric organic matters treated by the miniaturized chromatography device are connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector; the atmospheric organic matter pretreatment device for charge/proton ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector. The device can realize mutually assisted rapid qualitative and quantitative determination. The charge/proton soft ionization ionizes most of substances as molecular ion peaks, but can not identify isomers, and most of substances can be rapidly and qualitatively quantified after being combined with GC, but the substances with low proton affinity ionize out not as molecular ion peaks, so that the mass spectrogram is not easy to identify, and the detection mode of GC+EI can be sampled and identified by using a standard NIST spectrum library. The mode of combining the two can ensure the effective identification of the atmospheric organic matters, and avoids the phenomenon of mutual interference of overlapping peaks.
The miniaturized chromatographic device is shown in fig. 2, and comprises a metal cylinder (3), a quartz chromatographic column (2A), a synchronous heating device, a temperature sensor (1), a hollowed-out shell (5) and a fan (6), wherein the chromatographic column is a quartz capillary column, the synchronous heating device comprises an electromagnetic heating control board and an induction coil, the inner diameter of the quartz capillary column is 0.53mm, the length of the quartz capillary column is 5m, the quartz capillary column is a medium-polarity column, the metal cylinder is hollow, and the metal cylinder is made of tungsten.
As shown in fig. 5, at this time, the detection method is as follows: the specific implementation method comprises the following steps:
the system can realize accurate and rapid identification of atmospheric multicomponent organic matters, lock the specific information of high-concentration organic matters and provide data support for pollution sources and accurate tracing through a direct sample injection/sampling mode, a direct sample injection/purging mode, a switching mode, a GC rapid separation-measurement mode and a cooling standby mode.
The method specifically comprises the following steps:
GC-direct sample/EI-sampling mode: the computer interaction control system (16) controls the enrichment pipe (8) to be in a low-temperature collection state, and atmospheric samples are captured into the enrichment pipe (8) after passing through the electric three-way valve (7) under the suction action of the sampling pump (11), and the enrichment time is determined according to actual atmospheric samples. At the moment, the EI is in an isolated state, the driving slide block (17) is controlled to be in a closed state, and the EI area is completely isolated from the soft ionization area, so that mutual interference is reduced. The other atmospheric sample enters the GC through a second three-way valve (28) by the suction force of the mass spectrum, the isomer in the atmospheric sample is rapidly separated, the atmospheric sample directly enters a reaction zone of a CI source through a flow dividing valve (29), the two-way valve (27) is controlled to be in an open state, different reagents are selected according to sample information to enter a reagent ionization zone, generated reagent ions enter a subsequent reaction zone to carry out charge exchange or proton exchange plasma reaction with atmospheric sample molecules, and generated ions of the species to be detected are subjected to subsequent focusing by a lens group (24) and quantitative detection by a detector (26) after passing through a mass analysis component (25).
GC-direct injection/EI-purge mode: after the sampling is finished, the computer interaction control system (16) controls the enrichment pipe (8) to be still in a low-temperature acquisition state, and the carrier gas is discharged through the sampling pump (11) after passing through the electric three-way valve (7) and the enrichment pipe (8), so that oxygen and the like in the enrichment pipe (8) are purged and removed. At this time, the GC module, the soft ionization measurement mode, is in the direct sample injection detection stage.
Switching modes: and analyzing according to the measured substance information, selecting the substance information which cannot be directly identified, and designing a corresponding chromatographic column temperature programming method. In the switching mode, the isolation plate (18) is pulled open by the driving slide block (17) to leave a gas path channel, at the moment, the switching valve (20) is in a closed state, no reagent gas enters the ionization source, interference to EI ionization is avoided, and the two-way valve (28) is also in a closed state, and no sample enters.
EI-GC fast separation-measurement mode: the computer interaction control system (16) controls the enrichment pipe (8) to heat and raise the temperature, the carrier gas brings the organic matters to be detected enriched in the enrichment pipe (8) into the micro chromatographic device (12) for separation through the four-way valve (9) after passing through the electric three-way valve (7), the computer interaction control system (16) controls the electromagnetic controller to quickly raise the temperature of the chromatographic column according to a set temperature programming method, and the separated matters enter the EI ionization device (19) for ionization after passing through the flow dividing valve (29) and enter the subsequent modules for quantitative detection.
Cooling standby mode: after one round of measurement is completed, the computer interaction control system (16) controls the enrichment tube (8) and the miniaturized chromatographic device (12) to be in a low-temperature state, the isolation plate (18) is in a closed state, the reagent gas is in an open state, and the next sample injection ionization flow is waited.
Wherein the result based on EI ionization is similar to that of example 1.
The charge/proton ionization is integrated, so that the problem that certain compounds cannot be effectively ionized due to a specific ionization mechanism, so that detection cannot be realized can be solved, and the measurement of various substances can be realized. After charge/proton ionization is combined with a micro-chromatography system, an effective and rapid detection of complex compounds or compounds in which multiple isomers are present can be achieved. The combination of charge/proton ionization and a micro-chromatographic system has the advantages of rapid detection, multiple measurement species, high selectivity, structural information provision and wide applicability, and can be applied to a multi-scene substance rapid monitoring system.
Example 3
Embodiment 3 differs from embodiment 1 only in that the chromatographic column is a metal capillary column, specifically, the miniaturized chromatographic device is shown in fig. 1B, and comprises a metal chromatographic column, a synchronous heating device, a temperature sensor (1), a hollowed-out shell (5) and a fan (6), wherein the synchronous heating device comprises an electromagnetic heating control board and an induction coil, the inner diameter of the metal capillary column is 0.53mm, the length of the metal capillary column is 5m, and the metal capillary column is a medium polarity column. The procedure is as in example 1.
Wherein the result based on EI ionization is similar to that of example 1. But slightly delayed in time compared to example 1.
The results of charge/proton ionization are similar to those of the examples.
Comparative example 1
The prior art proton transfer reaction was used to ionize the aerosol material in the atmosphere for a measurement time of 30s. As a result, as shown in fig. 9, the method can effectively measure most substances, but the mass-to-charge ratio is taken as a measurement basis, so that the isomers cannot be identified. Indicating that the prior art is not capable of measuring certain substances.
The systems and methods of the present application can measure not only common atmospheric organics and inorganics, but also some specific substances, such as aerosol substances. The application range of the system and the method is wide, and the system and the method have universality.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but rather is capable of modification and variation without departing from the spirit and scope of the present invention as defined in the following claims.
Claims (18)
1. A miniaturized chromatographic device comprises a chromatographic column and a synchronous heating device,
The synchronous heating device directly or indirectly heats the chromatographic column in a non-contact mode, and the chromatographic column is a metal capillary column or a quartz capillary column.
2. The apparatus of claim 1, wherein,
the chromatographic column is a quartz capillary column, the synchronous heating device indirectly heats the chromatographic column,
the miniaturized chromatographic device further comprises a metal cylinder, the chromatographic column is wound outside the metal cylinder in a contact manner, and the synchronous heating device can enable the metal cylinder to generate heat to heat the chromatographic column.
3. The apparatus of claim 1, wherein,
the chromatographic column is a metal capillary column, the synchronous heating device directly heats the chromatographic column, and the synchronous heating device can enable the chromatographic column to heat itself so as to heat the chromatographic column.
4. The apparatus of claim 1, wherein,
the synchronous heating device can heat the chromatographic column to 30-500 ℃;
preferably, the synchronous heating device can enable the temperature rising rate of the chromatographic column to be 2-60 ℃/min, and the synchronous heating device can enable the temperature control precision of the chromatographic column to be +/-0.1 ℃.
5. The apparatus of claim 1, wherein,
the synchronous heating device comprises an electromagnetic heating control board and an induction coil, wherein the electromagnetic heating control board is connected with the induction coil, and the induction coil is arranged at the periphery of the chromatographic column in a non-contact mode so as to heat the chromatographic column.
6. The apparatus of claim 1, wherein,
the inner diameter of the quartz capillary column is 0.1 mm-0.6 mm, preferably any one of 0.53mm, 0.32mm, 0.25mm, 0.18mm and 0.1 mm;
the length of the quartz capillary column is 1 m-30 m; preferably any one of 2.5m, 5m, 10m and 15 m;
the quartz capillary column is selected from one or more of strong polar column, medium polar column, weak polar column and nonpolar column.
7. The apparatus of claim 1, wherein,
the inner diameter of the metal capillary column is 0.1 mm-0.6 mm, preferably any one of 0.2mm, 0.25mm, 0.32mm and 0.53mm,
the length of the metal capillary column is 1 m-30 m,
the metal capillary column is selected from one or more of strong polar column, medium polar column, weak polar column and nonpolar column.
8. The apparatus of claim 2, wherein,
The metal cylinder is hollow, and the material of the metal cylinder is one or more than two of tungsten, molybdenum, ferrosilicon alloy, ferronickel alloy and stainless steel.
9. The apparatus of claim 2 or 3, wherein,
the miniaturized chromatographic device further comprises a temperature sensor, wherein the temperature sensor is arranged between the metal cylinder and the chromatographic column and is used for displaying the temperature of the chromatographic column;
or,
the temperature sensor is arranged at the periphery of the chromatographic column and used for displaying the temperature of the chromatographic column.
10. The apparatus of claim 1, wherein,
the miniaturized chromatographic device further comprises a hollowed-out shell body, wherein the hollowed-out shell body is used for covering the metal cylinder and the chromatographic column or is used for covering the chromatographic column.
11. The apparatus of claim 1, wherein,
the miniaturized chromatography device further comprises a heat dissipation unit; the heat dissipation unit is positioned at the bottom of the hollowed-out shell;
preferably, the heat dissipation unit is a fan.
12. The apparatus of claim 3, wherein,
the volume of the miniaturized chromatographic device is 5cm 20cm 10cm 5cm 20 cm.
13. An atmospheric organic and/or inorganic matter measuring system comprising
The atmospheric organic pretreatment device is divided into an atmospheric organic pretreatment device for EI ionization and an atmospheric organic pretreatment device for charge/proton ionization;
Miniaturized chromatography device according to any one of claims 1 to 12, connected to an atmospheric organics pretreatment device for EI ionization and/or to an atmospheric organics pretreatment device for charge/proton ionization;
the ionization device is divided into an EI ionization device and a charge/proton ionization device, wherein the atmospheric organic matters treated by the miniaturized chromatographic device are connected with the inlet of the EI ionization device, and preferably, the atmospheric organic matters treated by the miniaturized chromatographic device are connected with the inlet of the charge/proton ionization device;
and the detection device is connected with the ionization device and is used for detecting the atmospheric organic matters ionized by EI and the atmospheric organic matters ionized by charge/protons.
14. The measurement system of claim 13, wherein,
the outlet of the EI ionization device is provided with a pair of isolation plates for controlling the entry and exit of the atmospheric organic matters ionized by the EI, each isolation plate is provided with a driving slide block, and the driving slide blocks are used for controlling the separation and the closing of the pair of isolation plates;
when the driving sliding block controls the pair of isolation plates to be separated, the atmospheric organic matters ionized by EI can enter the detection device for finely detecting the isomer matters;
When the driving sliding block controls the pair of isolation plates to be closed, the atmospheric organic matters ionized by EI can not enter the detection device, and the atmospheric organic matters ionized by charge/protons can enter the detection device for rapidly detecting the atmospheric organic matters and/or inorganic matters.
15. The measurement system of claim 13, wherein,
the atmospheric organic pretreatment device for EI ionization is used for sampling and purging, wherein the sampling is used for sampling atmospheric organic, and the purging is used for removing impurities in a pipeline;
the atmospheric organic pretreatment device for EI ionization sequentially comprises an atmospheric organic sample inlet and outlet pipeline, a three-way valve, a enrichment pipe, a four-way valve and a pump.
16. The measurement system of claim 13, wherein,
the atmospheric organic matter pretreatment device for EI ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector;
the atmospheric organic pretreatment device for charge/proton ionization is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector.
17. The measurement system of claim 13, wherein,
The atmospheric organic matter pretreatment device for EI ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the EI ionization device, and the EI ionization device is connected with the detector;
the atmospheric organic matter pretreatment device for charge/proton ionization is connected with the miniaturized chromatographic device, the atmospheric organic matter treated by the miniaturized chromatographic device is connected with the inlet of the charge/proton ionization device, and the charge/proton ionization device is connected with the detector.
18. A measurement method using the measurement system according to any one of claims 13 to 17, comprising:
sampling: introducing the atmospheric organics for EI ionization into an atmospheric organics pretreatment device for EI ionization; or, introducing the atmospheric organics for charge/proton ionization into an atmospheric organics pretreatment device for charge/proton ionization;
and (3) a purging step: purging an atmospheric organic pretreatment device for EI ionization and a transmission flow path;
and (3) sample injection: carrying the atmospheric organics treated by the atmospheric organics pretreatment device for EI ionization into a miniaturized chromatographic device and an EI ionization device; or, the atmospheric organic matter treated by the atmospheric organic matter pretreatment device for charge/proton ionization is brought into the miniaturized chromatographic device and the charge/proton ionization device;
The detection step comprises: separating and measuring the atmospheric organic matters subjected to EI ionization treatment; or, separating and measuring the atmospheric organic matters subjected to charge/proton ionization treatment;
or,
sampling: introducing the atmospheric organics for EI ionization into an atmospheric organics pretreatment device for EI ionization; or, introducing the atmospheric organics for charge/proton ionization into an atmospheric organics pretreatment device for charge/proton ionization;
and (3) a purging step: purging an atmospheric organic pretreatment device for EI ionization and a transmission flow path;
and (3) sample injection: carrying the atmospheric organics treated by the atmospheric organics pretreatment device for EI ionization into a miniaturized chromatographic device and an EI ionization device; or, carrying the atmospheric organic matters treated by the atmospheric organic matter pretreatment device for charge/proton ionization into the charge/proton ionization device;
the detection step comprises: separating and measuring the atmospheric organic matters subjected to EI ionization treatment; or, the atmospheric organic matter subjected to charge/proton ionization treatment is separated and measured.
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