CN106290210B - A kind of method and detection system of atmospheric pressure glow discharge detection metal ion - Google Patents
A kind of method and detection system of atmospheric pressure glow discharge detection metal ion Download PDFInfo
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- CN106290210B CN106290210B CN201610633194.8A CN201610633194A CN106290210B CN 106290210 B CN106290210 B CN 106290210B CN 201610633194 A CN201610633194 A CN 201610633194A CN 106290210 B CN106290210 B CN 106290210B
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- 238000001514 detection method Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 16
- 238000002417 atmospheric pressure glow discharge ionisation Methods 0.000 claims abstract description 70
- 239000012491 analyte Substances 0.000 claims abstract description 63
- 239000007789 gas Substances 0.000 claims abstract description 62
- 239000012159 carrier gas Substances 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 7
- 230000003068 static effect Effects 0.000 claims abstract description 3
- 150000004678 hydrides Chemical class 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000013307 optical fiber Substances 0.000 claims description 8
- 239000012488 sample solution Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 239000003708 ampul Substances 0.000 claims description 5
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 claims description 5
- 230000003595 spectral effect Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 19
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002203 pretreatment Methods 0.000 abstract description 4
- 238000010348 incorporation Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 9
- 230000005284 excitation Effects 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention provides the methods and detection system of a kind of atmospheric pressure glow discharge detection metal ion, it is captured and is enriched in inside APGD excitaton source online in situ by control oxygen incorporation realization analyte, and stops the gas supply of carrier gas, analyte gaseous species and oxygen after certain time preenrichment and close the inlet end of APGD excitaton source, 1~3s of interval is again turned on the inlet end of APGD excitaton source and restores the gas supply of carrier gas and analyte gaseous species, disturbance is generated to glow discharge plasma static environment inside APGD excitaton source, realizes the release of preenrichment analyte；By computer control solenoid valve " closed-open ", switching is generated rapidly for disturbance, and " enrichment-release " process can realize that software integrationization controls, precision and high degree of automation；The present invention greatly improves sample amounts detection and analysis efficiency instead of the pre-treatment Pre-enrichment of cumbersome time-consuming by studying Chinese on line technology in situ, and detection limit reduces an order of magnitude.
Description
Technical field
The present invention relates to the detection method of a metal ion species and detection systems, and in particular to a kind of atmospheric pressure glow discharge inspection
The method and detection system for surveying metal ion, belong to the spectrum analysis field of analytical chemistry.
Background technique
As mankind's activity includes agro-industry to the exploitation of all kinds of mineral metal products, smelting, processing and business manufacturing activities
It is increasing, metal ion pollution is increasingly severe.And it wherein contains the bio-toxicity in terms of environmental pollution and significantly weighs
Metallic element such as mercury, cadmium, lead, antimony, chromium and metalloid arsenic etc., is directly discharged into river, lake if heavy metal element is unprocessed
Pool or ocean, or enter soil in, due to they cannot be biodegradable and make these rivers, lake, ocean and soil by
To pollution, under the biomagnification of the food chain, their thousands of hundred times of ground enrichments finally enter human body and cause various harm.
Common metal detection at present relies on laboratory large-scale instrument analysis detection, including Atomic Absorption Spectrometer (AAS), original
Sub- emission spectrometer (ICP-AES), Atomic Fluorescence Spectrometer (AFS), X-ray fluorescence spectra analysis (XRF), inductive coupling etc. from
Daughter mass spectrograph (ICP-MS) etc..These laboratory large-scale instruments have that reliable test result, detection limit be low, high sensitivity level-one
The advantages such as multiple element detection, but big cumbersome, the expensive, inert gas of equipment instrument and gas consumption can be carried out simultaneously
High, energy consumption height and testing expense height etc., restricting it can only use in laboratory and (cannot achieve in-situ monitoring), while increase ring
Guaranteed cost.
Glow discharge (GD) is divided into two major classes: low pressure is to glow discharge and Atomospheric pressure glow discharge.Low pressure (50-
500Pa) glow discharge is mainly used for solid sample analysis, and the directly detection of fluid sample and gaseous sample became hot spot in recent years
Also normal pressure (atmospheric pressure) glow discharge (APGD) technology is promoted to rapidly develop.Atmospheric pressure glow discharge as a kind of miniature excitaton source with
Inductively coupled plasma body (ICP) excitaton source is compared, and has the advantages such as small in size, low in energy consumption, maintenance is simple, easy to operate, special
Micro metal detecting instrument Shi Yu not be researched and developed, the shortcoming of Laboratory Instruments can be made up well, thus has good development
Prospect.But APGD excitaton source reported at present still has certain gap with laboratory large-scale instrument in analysis performance, passes through sample
Element preenrichment (such as Solid Phase Extraction) to be measured is realized in product pre-treatment, can improve the analysis performance of APGD, but other can be brought to lack
It falls into (complex steps, operation is harsh, time-consuming), how simply and effectively further promotion APGD analysis performance, which becomes, urgently solves
Certainly the problem of.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provide a kind of atmospheric pressure glow discharge detection metal ion method and
Detection system examines sample amounts by studying Chinese on line technology in situ instead of the pre-treatment Pre-enrichment of cumbersome time-consuming
It surveys analysis efficiency to greatly improve, realizes and analyte analyzation ability is substantially improved.
Realize that technical solution used by the object of the invention is, a kind of method of atmospheric pressure glow discharge detection metal ion,
The following steps are included:
(1) carrier gas is full of in APGD excitaton source；
(2) APGD excitaton source igniting generates atmospheric pressure glow discharge, and adjustings power supply is constant current mode, electric current stabilization 20~
40mA, voltage range are 500~1000V；
(3) sample solution is introduced into hydride generator, sample solution reacts in hydride generator generates analyte
Gaseous species, by carrier gas by analyte gaseous species take out of and and oxygen mix, above-mentioned mixed gas is continually fed into
Preenrichment is carried out in APGD excitaton source, the particular content of preenrichment is that the analyte gaseous species in mixed gas are tieed up in electric discharge
Complex reaction occurs under the plasma environment held and generates preenrichment analyte, preenrichment analyte is sunk inside APGD excitaton source
Product enrichment；
(4) after preenrichment, stop the gas supply of carrier gas, analyte gaseous species and oxygen and close the air inlet of APGD excitaton source
End opens the inlet end of APGD excitaton source after being spaced 1~3s and restores the gas supply of carrier gas and analyte gaseous species, and carrier gas will divide
Analysis object gaseous species in hydride generator from taking out of into APGD excitaton source；
(5) pass through the transmitting characteristic spectral line of optical fiber and CCD spectrometer collection preenrichment analyte, CCD spectrometer will acquire
Signal is transferred to computer and is detected, and obtains testing result.
Carrier gas described in step (1) is one or more kinds of mixed carrier gas of argon gas, helium, neon, nitrogen
The preenrichment time described in step (3) is 1s~600s.
In step (3) mixed gas by APGD excitaton source cathode introduce, flow to anode after be discharged.
In step (4) carrier gas by analyte gaseous species from being taken out of in hydride generator into APGD excitaton source, by
The cathode introducing of APGD excitaton source is discharged after flowing to anode.
The also corresponding detection system provided for the above method of the present invention, includes at least gas source component, hydride occurs
Device, APGD excitaton source, optical fiber and CCD spectrometer, gas source component and hydride generator are connected to APGD excitaton source, the gas
Source component includes carrier gas gas cylinder, carrier gas air supply pipe, oxygen gas cylinder, oxygen air supply pipe, threeway, analyte air supply pipe and mixed gas
Air supply pipe, oxygen air supply pipe, analyte air supply pipe and mixed gas air supply pipe respectively with three open communications of threeway, hydride
The air inlet and air outlet of generator are separately connected carrier gas air supply pipe and analyte air supply pipe, and oxygen air supply pipe and mixed gas supply
Solenoid valve A and solenoid valve B are separately installed on tracheae；Further include computer, CCD spectrometer, solenoid valve A and solenoid valve B with
Computer is electrically connected.
The APGD excitaton source is by high-voltage DC power supply, current-limiting resistance, metal electrode, quartz ampoule and polytetrafluoro pedestal structure
At high-voltage DC power supply, current-limiting resistance and metal electrode are connected by conducting wire.
The metal electrode includes cathode tube and anode tube, cathode tube and anode 1~50mm of tube spacing, cathode tube and anode
Pipe is hollow titanium metal pipe, and cathode tube is inlet end, 20~100mm of cathode pipe range, 2~10mm of outer diameter, 0.2~5mm of wall thickness,
5~100mm of anode pipe range, 2~20mm of outer diameter, 0.2~10mm of wall thickness.
Quartz the pipe range 20~200mm, 2~20mm of outer diameter, 0.2~10mm of wall thickness.
The carrier gas gas cylinder and oxygen gas cylinder are both secured in roll-over protective structure.
As shown from the above technical solution, the present invention realizes that analyte is captured and is enriched with online in situ by control oxygen incorporation
In the electrode surface or quartzy inside pipe wall of APGD excitaton source, and stop carrier gas, analyte gaseous state object after certain time preenrichment
The gas supply of kind and oxygen and the inlet end for closing APGD excitaton source, 1~3s of interval are again turned on the inlet end of APGD excitaton source simultaneously
Restore the gas supply of carrier gas and analyte gaseous species, carrier gas takes analyte gaseous species from hydride generator to APGD out of
The carrier gas flowed in the process in excitaton source and analyte gaseous species are to glow discharge plasma inside APGD excitaton source
Static environment is disturbed, realize preenrichment analyte release, preenrichment analyte enter electric discharge of APGD excitaton source etc. from
Daughter area is excited, and the present invention makes sample instead of the pre-treatment Pre-enrichment of cumbersome time-consuming by studying Chinese on line technology in situ
Product quantitative detecting analysis efficiency greatly improves, and realizes and (detection limit one number of reduction is substantially improved to analyte analyzation ability
Magnitude).
By computer control solenoid valve " closed-open ", switching is generated rapidly for above-mentioned disturbance, and apparatus structure is simply easy
In operation, substantially without fringe cost (testing cost as caused by " enrichment-release " process), " enrichment-release " process can be realized
Software integrationization control, precision and high degree of automation.
The present invention is based on beneficial effects possessed by its technical solution to be:
(1) solenoid valve " open-close " is controlled by computer terminal when detection system of the invention operation, completes analyte
Gaseous species are easy to operate in the online preenrichment in situ of APGD excitaton source and release detection, high degree of automation；
(2) analyte gaseous species can be completed in situ online in APGD excitaton source when detection system of the invention operation
Preenrichment and release detection, sample analysis is high-efficient, significantly improves APGD analysis performance, improves sensitivity；
(3) detection system APGD excitaton source cathode inlet of the invention design, improves the discharge stability of excitaton source, solves
The requirement that cathode of having determined overheat and the strong sputtering and cathode material loss caused also reduce electrode material performance makes electrode material
Expect that range of choice is wider；
(4) current-limiting resistance is used in circuit, to protection power source and direct current glow discharge is maintained to put it to electric arc
Electricity transformation, to improve the stability of spectral signal；
(5) method of the atmospheric pressure glow discharge detection metal ion of offer of the invention is simple and easy, using of the invention
Detection system can be obviously improved APGD excitaton source analysis performance, reduce analysis cost, improve analysis efficiency, and can ensure that analyte
Element detection has good accuracy and repeatability.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of detection system provided by the invention.
Fig. 2 is the structural schematic diagram of APGD excitation component.
Fig. 3 is that studying Chinese on line method provided by the invention is examined with existing normal detection method using Ar as carrier gas
Survey the emission spectrum signal contrast figure of 1ng/mL As standard solution.
Fig. 4 is that studying Chinese on line method provided by the invention is examined with existing normal detection method using Ar as carrier gas
Survey the emission spectrum signal contrast figure of 1ng/mL Sb standard solution.
Wherein, 1- carrier gas gas cylinder, 2- oxygen gas cylinder, 3- solenoid valve A, 4- hydride generator, 5- solenoid valve B, 6- high pressure
DC power supply, 7- threeway, 8- current-limiting resistance, 9-APGD excitation component, 91- cathode tube, 92- anode tube, 93- quartz ampoule, 94- are poly-
Tetrafluoro pedestal, 10- fibre-optical probe, 11-CCD spectrometer, 12- computer, 13- optical fiber, 14- carrier gas air supply pipe, 15- oxygen gas supply
Pipe, 16- analyte air supply pipe, 17- mixed gas air supply pipe, 18- roll-over protective structure.
Specific embodiment
The present invention is illustrated in detail with reference to the accompanying drawings and examples, the contents of the present invention are not limited to following
Embodiment.
The present invention provides a kind of methods of atmospheric pressure glow discharge detection metal ion, comprising the following steps:
(1) argon gas is full of by APGD excitaton source with the flow velocity of 300mL/min；
(2) APGD excitaton source igniting generates atmospheric pressure glow discharge, and adjustings power supply is constant current mode, electric current stabilization 20~
40mA, voltage range are 500~1000V；
(3) sample solution is introduced into hydride generator, sample solution reacts in hydride generator generates analyte
Gaseous species, by argon gas by analyte gaseous species take out of and and oxygen mix, above-mentioned mixed gas is continually fed into
Preenrichment, preenrichment time 1s~600s are carried out in APGD excitaton source, the particular content of preenrichment is that mixed gas is swashed by APGD
The cathode to rise introduces, and the analyte gaseous species in mixed gas occur complicated anti-under the plasma environment that electric discharge maintains
Preenrichment analyte should be generated, preenrichment analyte deposits enrichment inside APGD excitaton source, and residual gas flows to anode heel row
Out；
(4) after preenrichment, stop the gas supply of argon gas, analyte gaseous species and oxygen and close the air inlet of APGD excitaton source
End opens the inlet end of APGD excitaton source after being spaced 1~3s and restores the gas supply of argon gas and analyte gaseous species, and argon gas will divide
Object gaseous species are analysed from being taken out of in hydride generator into APGD excitaton source, argon gas is excited with analyte gaseous species by APGD
The cathode in source introduces, and complex reaction occurs under the plasma environment that electric discharge maintains and generates preenrichment point for analyte gaseous species
Object is analysed, preenrichment analyte deposits enrichment inside APGD excitaton source, and residual gas is discharged after flowing to anode；
(5) pass through the transmitting characteristic spectral line of optical fiber and CCD spectrometer collection preenrichment analyte, CCD spectrometer will acquire
Signal is transferred to computer and is detected, and obtains testing result.
The comparison of the test result of detection method and the prior art is as shown in Figure 3 and Figure 4.Fig. 3 is spectrometer unicast
The time spectra signal graph of long (As 193.7nm) acquisition, abscissa are the quantity of sampling site signal value increase with time
(Count), ordinate is signal value (a.u).When normally being detected using the prior art, 1ng/mL As is unchanged at any time
(being worth in no signal undetectable) can stop argon gas and divide when using the method for the present invention to carry out preenrichment and release process
Analysis object gaseous species gas supply (closing solenoid valve B) starts and the signal value of As 193.7nm occurs in certain the subsequent time, intuitively
The present invention has been reacted to be obviously improved APGD excitaton source analysis performance.Fig. 4 is same as above, and is two kinds of detection effects of 1ng/mL Sb
Comparison diagram.
The also corresponding detection system provided for the above method of the present invention, structure is as shown in Figure 1, include gas source group
Part, hydride generator 4, APGD excitaton source, optical fiber 13, CCD spectrometer 11 and computer 12, gas source component and hydride occur
Device is connected to APGD excitaton source；The gas source component includes carrier gas gas cylinder 1, carrier gas air supply pipe 14, oxygen gas cylinder 2, oxygen confession
Tracheae 15, threeway 7, analyte air supply pipe 16 and mixed gas air supply pipe 17, carrier gas gas cylinder 1 and oxygen gas cylinder 2 are both secured to pacify
In full frame 18, oxygen air supply pipe 15, analyte air supply pipe 16 and mixed gas air supply pipe 17 connect with three openings of threeway 7 respectively
Logical, the air inlet and air outlet of hydride generator 4 are separately connected carrier gas air supply pipe 14 and analyte air supply pipe 16, oxygen gas supply
Solenoid valve A3 and solenoid valve B5, CCD spectrometer, solenoid valve A and electromagnetism are separately installed on pipe 15 and mixed gas air supply pipe 17
Valve B is electrically connected with computer；
The APGD excitaton source improves on the basis of existing atmospheric pressure glow discharge plasma excitaton source, by high pressure
DC power supply 6, current-limiting resistance 8 and APGD excitation component 9 are in series by conducting wire, referring to fig. 2, the APGD excitation component 9
It is made of cathode tube 91, anode tube 92, quartz ampoule 93 and polytetrafluoro pedestal 94, cathode tube and anode tube are hollow titanium
Pipe, 92 1~50mm of spacing of cathode tube 91 and anode tube, cathode tube are inlet end, are fixed by polytetrafluoro pedestal 94, the light of optical fiber
The outlet side of 10 alignment quartz ampoule 93 of fibre probe and anode tube 92,20~100mm of cathode pipe range, 2~10mm of outer diameter, wall thickness 0.2
~5mm, 5~100mm of anode pipe range, 2~20mm of outer diameter, wall thickness 0.2~10mm, quartzy 20~200mm of pipe range, outer diameter 2~
20mm, 0.2~10mm of wall thickness, high-voltage DC power supply, current-limiting resistance and metal electrode are connected by conducting wire.
The detection system can be used for the Element detections such as As and Sb in sample solution, specific steps are as follows:
(1) the solenoid valve A in oxygen gas circuit is closed, the solenoid valve B between threeway and APGD excitaton source is opened, with 300mL/
Ar carrier gas is full of pipeline and APGD excitaton source by the flow velocity of min；
(2) APGD excitaton source igniting generates atmospheric pressure glow discharge, and adjusting power supply is that constant current mode electric current is stablized in 30mA,
700~1000V of voltage range at this time；
(3) sample solution, which introduces hydride generator and reacts, generates analyte gaseous species, analyte gaseous species quilt
Ar carrier gas takes out of and passes through threeway and mixes with oxygen (solenoid valve A is open state at this time), and above-mentioned mixed gas enters APGD and swashs
It rises, analyte gaseous species occur complex reaction and sink in electrode and quartzy tube wall in the plasma environment maintained that discharges
Product enrichment；
(4) after a period of time (60s), solenoid valve A and solenoid valve B is closed, is spaced opens solenoid valve B after 1s, the process
Gas disturbance realizes that preenrichment analyte discharges and enters discharge plasma area and is excited that analyte emits characteristic spectral line and passes through
The detection of CCD spectrometer collection.
Detection system structure of the invention is simple, adds solenoid valve A and solenoid valve B, can be arranged by computer and realize automation
Control.Detection system of the invention is particularly suitable for detection hydride and system elements such as As, Cd and Sb etc. occurs.Use the present invention
Detection system be greatly improved the sensitivity of APGD excitaton source, reduce analysis cost, improve analysis efficiency and can ensure that every kind
The accuracy and repeatability of Element detection.
Claims (10)
1. a kind of method of atmospheric pressure glow discharge detection metal ion, which comprises the following steps:
(1) carrier gas is full of in APGD excitaton source；
(2) igniting of APGD excitaton source generates atmospheric pressure glow discharge, and adjusting power supply is constant current mode, and electric current is stablized in 20~40mA,
Voltage range is 500~1000V；
(3) sample solution is introduced into hydride generator, sample solution reacts in hydride generator generates analyte gaseous state
Species, by carrier gas by analyte gaseous species take out of and and oxygen mix, above-mentioned mixed gas is continually fed into APGD and is swashed
Rise middle carry out preenrichment, and the particular content of preenrichment is, the analyte gaseous species in mixed gas electric discharge maintain etc.
Gas ions environment issues raw complex reaction and generates preenrichment analyte, and preenrichment analyte deposits richness inside APGD excitaton source
Collection；
(4) after preenrichment, the gas supply of carrier gas, analyte gaseous species and oxygen is stopped by solenoid valve and closes APGD excitaton source
Inlet end, be spaced 1~3s after by solenoid valve unlatching APGD excitaton source inlet end and restore carrier gas and analyte gaseous state object
The gas supply of kind, carrier gas from being taken out of in hydride generator into APGD excitaton source, in the process, lead to analyte gaseous species
It crosses the rapid off/on switching of computer control solenoid valve and the carrier gas of flowing and analyte gaseous species excites APGD
Glow discharge plasma static environment is disturbed inside source, realizes the release of preenrichment analyte, preenrichment analyte into
The discharge plasma area for entering APGD excitaton source is excited；
(5) pass through the transmitting characteristic spectral line of optical fiber and CCD spectrometer collection preenrichment analyte, CCD spectrometer will acquire signal
It is transferred to computer to be detected, obtains testing result.
2. the method for atmospheric pressure glow discharge detection metal ion according to claim 1, it is characterised in that: in step (1)
The carrier gas is one or more kinds of mixed carrier gas of argon gas, helium, neon, nitrogen.
3. the method for atmospheric pressure glow discharge detection metal ion according to claim 1, it is characterised in that: in step (3)
The preenrichment time is 1~600s.
4. the method for atmospheric pressure glow discharge detection metal ion according to claim 1, it is characterised in that: in step (3)
Mixed gas by APGD excitaton source cathode introduce, flow to anode after be discharged.
5. the method for atmospheric pressure glow discharge detection metal ion according to claim 1, it is characterised in that: in step (4)
Carrier gas from being taken out of in hydride generator into APGD excitaton source, is drawn analyte gaseous species by the cathode of APGD excitaton source
Enter, flow to anode after be discharged.
6. a kind of detection system of the method for the detection metal ion of atmospheric pressure glow discharge described in claim 1, includes at least
Gas source component, hydride generator, APGD excitaton source, optical fiber and CCD spectrometer, gas source component and hydride generator with
APGD excitaton source connection, it is characterised in that: the gas source component includes carrier gas gas cylinder, carrier gas air supply pipe, oxygen gas cylinder, oxygen confession
Tracheae, threeway, analyte air supply pipe and mixed gas air supply pipe, oxygen air supply pipe, analyte air supply pipe and mixed gas gas supply
Pipe respectively with three open communications of threeway, the air inlet and air outlet of hydride generator be separately connected carrier gas air supply pipe and point
Object air supply pipe is analysed, is separately installed with solenoid valve A and solenoid valve B on oxygen air supply pipe and mixed gas air supply pipe；It further include calculating
Machine, CCD spectrometer, solenoid valve A and solenoid valve B are electrically connected with computer.
7. detection system according to claim 6, it is characterised in that: the APGD excitaton source is by high-voltage DC power supply, limit
Leakage resistance, metal electrode, quartz ampoule and polytetrafluoro pedestal are constituted, and high-voltage DC power supply, current-limiting resistance and metal electrode are by leading
Line series connection.
8. detection system according to claim 7, it is characterised in that: the metal electrode includes cathode tube and anode tube,
Cathode tube and anode 1~50mm of tube spacing, cathode tube and anode tube are hollow titanium metal pipe, and cathode tube is inlet end, cathode
20~100mm of pipe range, 2~10mm of outer diameter, 0.2~5mm of wall thickness, 5~100mm of anode pipe range, 2~20mm of outer diameter, wall thickness 0.2~
10mm。
9. detection system according to claim 8, it is characterised in that: the quartz 20~200mm of pipe range, outer diameter 2~
20mm, 0.2~10mm of wall thickness.
10. detection system according to claim 6, it is characterised in that: the carrier gas gas cylinder and oxygen gas cylinder are both secured to
In roll-over protective structure.
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| CN110793958B (en) * | 2018-08-01 | 2021-06-15 | 中国科学院上海硅酸盐研究所 | Hydride generation-atmospheric pressure glow discharge atomic spectrum device |
| CN110797252B (en) * | 2018-08-01 | 2020-10-23 | 中国科学院上海硅酸盐研究所 | Atmospheric glow discharge ion source device |
| CN109406493A (en) * | 2018-09-21 | 2019-03-01 | 中国地质大学（武汉） | A kind of portable fluid cathode glow discharging heavy metal detector and detection method |
| CN111929290A (en) * | 2019-05-13 | 2020-11-13 | 中国科学院上海硅酸盐研究所 | Atomic emission spectrum device of tungsten filament electric heating evaporation-atmospheric pressure glow discharge |
| CN113720811B (en) * | 2021-08-19 | 2022-12-30 | 中国地质大学（武汉） | Micro-plasma excitation source and excitation method based on ultrasonic atomization sampling |
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