CN102033103A - Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device - Google Patents
Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device Download PDFInfo
- Publication number
- CN102033103A CN102033103A CN2010105203521A CN201010520352A CN102033103A CN 102033103 A CN102033103 A CN 102033103A CN 2010105203521 A CN2010105203521 A CN 2010105203521A CN 201010520352 A CN201010520352 A CN 201010520352A CN 102033103 A CN102033103 A CN 102033103A
- Authority
- CN
- China
- Prior art keywords
- mercury
- discharge
- liquid
- gas
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/67—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using electric arcs or discharges
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
- G01N21/6404—Atomic fluorescence
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/69—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence specially adapted for fluids, e.g. molten metal
Landscapes
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Optics & Photonics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a mercury morphological analysis method based on liquid cathode discharge and a mercury vapor generating device. The method comprises: a mercury-containing sample solution is introduced into a chromatographic column of a liquid chromatograph; a discharge medium carrier flow passes through a sample introduction device and is introduced into a sample introduction capillary tube of a discharge pool with the effluence of the chromatographic column through a tee joint; by taking a metal electrode as an anode, and graphite, platinum or a stainless steel material as a cathode, liquid cathode discharging is carried out to generate vapor which is carried by a carrier gas into a gas-liquid separator; and finally the separated gas is detected by an atomic fluorescence spectrometer to obtain the morphology of mercury. Through the method provided by the invention, organic mercury and inorganic mercury in an object to be detected are effectively separated and detected; and the method has the advantages of small volume, low energy consumption, high mercury vapor generation efficiency and low matrix interference, is simple in operation and can be used for analyzing the morphology of mercury in a biological sample.
Description
Technical field
The present invention relates to a kind of mercury morphological analysis method and mercury vapour generating means, belong to analytical chemistry morphological analysis field based on the liquid cathode discharge.
Background technology
The morphological analysis method of mercury generally adopts method for combined use to realize.It at first utilizes chromatogram to realize the separation of different mercury shapes, utilizes sensitive element selective detector to realize detecting then.Wherein, high performance liquid chromatography and atomic spectrum instrument especially atomic fluorescence method for combined use are common mercury morphological analysis methods, and this is because atomic fluorescence has good, the highly sensitive advantage of selectivity.Its principle is: after adopting atomic fluorescence to detect, each fluorescence peak is represented a kind of form of mercury, it is the corresponding different retention time of mercury of different shape, the retention time of three kinds of mercury in the retention time of three kinds of mercury in the sample solution and the standard spectrogram is compared, the retention time unanimity be form with a kind of mercury.In HPLC-CV-AFS detection technique in the past, organic mercury normally adopts the method realization of post rear oxidation agent on-line oxidation to clear up.Though chemical oxidation can at room temperature be finished, need the sufficient reaction time to realize transforming the adding that needs chemical reagent simultaneously.The development of ultraviolet oxidation technology can make organic mercury be oxidized to the adding that inorganic mercury need not oxygenant, but makes apparatus complicated more.
And liquid cathode discharge (solution cathode glow discharge, SCGD) then provide a kind of new mercuryvapour method for generation, it can make reduction step in discharge process of organomercurial oxidation and inorganic mercury finish, and has avoided the adding of redox reagent.Electric discharge device adopts electrolytic solution as negative electrode, and metal electrode places several millimeters places, solution top as anode.High energy particle that produces in the discharge process such as the OH in the water and H can with test substance generation redox reaction, thereby eliminated the adding that adds redox reagent.Produce because the discharge steam takes place by moment, thereby can carry out coupling with flow injection and liquid chromatography.
Summary of the invention
The objective of the invention is to remedy the deficiency of existing mercury morphological analysis method, a kind of mercury morphological analysis method and mercury vapour generating means based on the liquid cathode discharge is provided, this method utilizes free radical in the plasma of liquid cathode discharge generation and organic mercury and inorganic mercury to produce reaction, make organic mercury and inorganic mercury all be converted into the nonvalent mercury steam, and realize the morphological analysis of mercury with liquid chromatography and atomic fluorescence coupling, have simple to operate, advantages such as volume is little, low energy consumption, can be used for the morphological analysis of biological sample mercury.
Realize that the technical scheme that the object of the invention adopted is:
A kind of mercury morphological analysis method based on the liquid cathode discharge, this method is: the testing sample solution that will contain mercury is introduced in the chromatographic column of liquid chromatograph, the discharge medium current-carrying then is incorporated in the sample introduction kapillary in discharge pond by sampling device with the effluent of chromatographic column by threeway, with the metal electrode is anode, with graphite, platinum or stainless steel material are negative electrode, anode and sample introduction arcing distance capillaceous is 0.5mm～3.0mm, adopt direct supply, at discharge current is to carry out liquid cathode discharge generation steam under 20mA～90mA condition, the steam that makes discharge generation then enters under carrier gas drives and carries out gas-liquid separation in the gas-liquid separator, adopt atomic fluorescence spectrometer that isolated gas is carried out the fluoroscopic examination analysis, can draw the form of mercury; Described discharge medium is any or several potpourri in nitric acid, sulfuric acid or the phosphoric acid, and the pH value of discharge medium is 1.0～3.0.
And, the flow velocity of discharge medium current-carrying is 1.0ml/min～2.0ml/min, the voltage of direct supply is 500V～1200V, carrier gas is any or several mixed gas in air, nitrogen, helium, argon gas or the oxygen, flow rate of carrier gas is 200ml/min～800ml/min, gas-liquid separator is circumscribed with recirculated cooling water, and the temperature of chilled water is 0.1 ℃～5 ℃.
And, containing organic acid, alcohol, ketone or alkane in the discharge medium, this organic acid, alcohol, ketone or the alkane concentration of volume percent in discharge medium is 0.1%～2.0%.
The present invention also provides a kind of used mercury vapour generating means of mercury morphological analysis method based on the liquid cathode discharge, this device is airtight liquid cathode discharge pond, the upper and lower in discharge pond is respectively equipped with anode and negative electrode, circuit connects direct supply by two electrodes and constitutes, the bottom in discharge pond is provided with the sample introduction kapillary, it is relative with anode that a sample introduction end capillaceous is positioned at the discharge pond, its other end is positioned at discharge outside, pond, anode and sample introduction arcing distance capillaceous is 0.5mm～3.0mm, the side wall upper part in discharge pond is provided with gas vent, and its underpart is provided with carrier gas inlet and waste liquid outlet.
And anode is a metal electrode, and the material of metal electrode is any or several alloy in platinum, tungsten or the titanium, and the material of negative electrode is graphite, platinum or stainless steel.
And the voltage of direct supply is 500V～1200V.
And, be provided with the porcelain tube resistance of a 1K Ω～5K Ω in the circuit.
And sample introduction internal diameter capillaceous is 0.1mm～0.5mm.
Mercury morphological analysis method of the present invention is to be anode with the metal electrode, the sample solution that contains mercury serves as the discharge negative electrode, adopt direct supply to discharge, utilize the existence of a large amount of high energy particles in the discharge plasma to cause plasma chemical reaction, thereby under the situation that does not add any redox reagent, can realize the steam generation of element mercury.The reduction of the oxidation of methyl mercury and ethyl mercury and divalence inorganic mercury can be finished in a step in the process of discharge, so with the coupling realization of atomic fluorescence spectrometer and liquid chromatography morphological analysis to three kinds of mercury (methyl mercury, ethyl mercury, divalence inorganic mercury).Compared with prior art, advantage of the present invention is as follows:
One step of reduction of organomercurial oxidation and inorganic mercury finishes in the discharge process of the inventive method, need not to add redox reagent, can realize effectively separating and detecting of organic mercury and inorganic mercury in the determinand, and can under atmospheric pressure realize, it is little to have equipment volume, low energy consumption, simple operation and other advantages, the efficient height of mercuryvapour generation simultaneously, matrix disturb little, can be used for the research as mercury morphological analysis in the biological samples such as tuna, inkfish and shrimp.
Description of drawings
Fig. 1 is the structural representation of mercuryvapour generating means of the present invention;
Fig. 2 is the device synoptic diagram of mercuryvapour generating means of the present invention and liquid chromatography and atomic fluorescence spectrometer coupling;
Fig. 3 is the standard spectrogram of methyl mercury, ethyl mercury and the inorganic mercury of 100 μ g/l, A: the fluorescence peak of methyl mercury for detectable concentration; B: the fluorescence peak of inorganic mercury; C: the fluorescence peak of ethyl mercury;
Among the figure, 1: the discharge pond; 2: anode; 3: negative electrode; 4: the sample introduction kapillary; 5: gas vent; 6: carrier gas inlet; 7: waste liquid outlet; 8: direct supply; 9: porcelain tube resistance; 10: the chromatogram pump; 11: injection annulus; 12: chromatographic column; 13: peristaltic pump; 14: threeway; 15: gas-liquid separator; 16: atomic fluorescence spectrometer.
Embodiment
The present invention is further illustrated below by specific embodiment, but protection content of the present invention is not limited to following examples.
As shown in Figure 1, the mercury vapour generating means that the present invention is based on the liquid cathode discharge is an airtight liquid cathode discharge pond 1, the upper and lower in discharge pond 1 is respectively equipped with anode 2 and negative electrode 3, anode 2 is a metal electrode, can adopt tungsten, in titanium or the platinum any or several alloy are as the electrode material of anode 2, negative electrode 3 used materials are graphite, platinum or stainless steel, circuit connects direct supply 8 by two electrodes and constitutes, the voltage of direct supply 8 is 500V～1200V, discharge current is 20mA～90mA, and the porcelain tube resistance 9 that can establish a 1K Ω～5K Ω in circuit is to realize stable discharging.The bottom in discharge pond 1 is provided with sample introduction kapillary 4, its internal diameter is 0.1mm～0.5mm, it is relative with anode 2 that one end of sample introduction kapillary 4 is positioned at discharge pond 1, its other end is positioned at the outside in discharge pond 1, the sample solution that contains mercury enters in the sample introduction kapillary 4, serve as the discharge negative electrode, the distance between anode 2 tips and sample introduction kapillary 4 tops (being the arcing distance of anode 2 and sample introduction kapillary 4) is 0.5mm～3.0mm.The side wall upper part in discharge pond 1 is provided with gas vent 5, and its underpart is provided with carrier gas inlet 6 and waste liquid outlet 7, and carrier gas is any in air, nitrogen, helium, argon gas or the oxygen, also can be the mixed gas of any several gases wherein.
The mercury morphological analysis method that the present invention is based on the liquid cathode discharge is:
By chromatogram pump 10 testing sample solution that contains mercury in the injection annulus 11 is incorporated in the chromatographic column 12 of liquid chromatograph (also can adopt other input modes commonly used), with nitric acid, in sulfuric acid or the phosphoric acid any or several potpourri are as discharge medium, the pH value of discharge medium is 1.0～3.0, can in discharge medium, add organic acid, alcohol, ketone or alkane, this organic acid, alcohol, ketone or the alkane concentration of volume percent in discharge medium is 0.1%～0.2%, adds organic acid, alcohol, ketone or alkane can strengthen the efficient of mercury vapour generation and then fluorescence signal is strengthened.Adopting peristaltic pump 13 (also can adopt other sampling devices) that the discharge medium current-carrying is incorporated in the sample introduction kapillary 4 in discharge pond 1 by a threeway 14 with the flow velocity of the 1.0ml/min～2.0ml/min effluent with chromatographic column 12, is that 500V～1200V, discharge current are to carry out liquid cathode discharge generation steam under 20mA～90mA condition at sparking voltage.With any or several mixed gas in air, nitrogen, helium, argon gas or the oxygen as carrier gas, feed carrier gas by carrier gas inlet 6, flow rate of carrier gas is 200ml/min～800ml/min, the steam of discharge generation enters in the gas-liquid separator 15 that is circumscribed with recirculated cooling water under carrier gas drives and carries out gas-liquid separation, cooling water temperature is 0.1 ℃～5 ℃, gaseous material after the separation enters atomic fluorescence spectrometer 16 and carries out check and analysis, draw the form of mercury in the sample solution, the waste liquid that discharge pond 1 and gas-liquid separator 15 produce all passes through another peristaltic pump and discharges.The used device synoptic diagram of this method is seen Fig. 2.
The percent concentration of each material all refers to the percent concentration that it is shared in moving phase in following examples moving phase.
Embodiment 1:
Choose tungsten bar as anode, cathode material is chosen platinum filament.The intercapillary arcing distance of anode and sample introduction is 2.0mm, and sample introduction internal diameter capillaceous is 0.18mm, and discharge medium is a nitric acid, and the pH value is 1.3, and the flow velocity of discharge medium current-carrying is 1.5ml/min.The voltage of direct supply adopts 1000V, discharge current 55mA.Argon gas is adopted in carrier gas, and flow velocity is 400ml/min.Liquid-phase chromatographic column is ZORBAX SB-C18 post (2.1 * 50mm, 5 μ m), and liquid chromatography moving phase is ammonium acetate+0.1% (v/v) mercaptoethanol of 0.06mol/l, and flow rate of mobile phase is 0.4ml/min.The signal of three kinds of mercury detects with atomic fluorescence.Experiment finds that detection signal is with the linear variation of sample concentration.Fig. 3 is the standard spectrogram of the methyl mercury that adopts the inventive method to measure concentration to be 100 μ g/l, ethyl mercury, inorganic mercury.
Embodiment 2:
Choose the titanium rod as anode, cathode material is chosen graphite.The intercapillary arcing distance of anode and sample introduction is 0.5mm, and sample introduction internal diameter capillaceous is 0.1mm, and discharge medium is a sulfuric acid, and the pH value is 2.0, and the flow velocity of discharge medium current-carrying is 1.0ml/min.The voltage of direct supply adopts 500V, discharge current 20mA.Air is adopted in carrier gas, and flow velocity is 200ml/min.Liquid-phase chromatographic column is Dikma-C18 post (4.6 * 150mm, 5 μ m), and liquid chromatography moving phase is: 5% (v/v) acetonitrile+0.462% (m/v) ammonium acetate+0.12% (m/v) halfcystine, flow rate of mobile phase is 1.0ml/min.Detect three kinds of mercury signals in the inkfish sample with atomic fluorescence, signal is with the linear variation of different sample concentrations.
Embodiment 3:
Choose the platinum titanium alloy as anode, cathode material is chosen stainless steel.The intercapillary arcing distance of anode and sample introduction is 2mm, sample introduction internal diameter capillaceous is 0.3mm, discharge medium is phosphoric acid+0.1% (v/v) formic acid (being meant that herein the concentration of volume percent of formic acid in discharge medium is 0.1%), the pH value is 2.5, and the flow velocity of discharge medium current-carrying is 2ml/min.The voltage of direct supply adopts 1200V, discharge current 90mA.Helium is adopted in carrier gas, and flow velocity is 800ml/min.Liquid-phase chromatographic column is CLC-ODS C18 post (150 * 6mm, 10 μ m), and moving phase is 50% (v/v) methyl alcohol+10mmol l
-1Tetrabutyl ammonium bromide+0.1mol l
-1Sodium chloride, flow rate of mobile phase are 1.2ml/min.Detect three kinds of mercury signals in the tuna sample with atomic fluorescence, signal is with the linear variation of different sample concentrations.
Embodiment 4:
Choose tungsten as anode, cathode material is chosen graphite.The intercapillary arcing distance of anode and sample introduction is 3mm, and sample introduction internal diameter capillaceous is 0.25mm, and discharge medium is the mixed solution of phosphoric acid and nitric acid, and the pH value is 1, and the flow velocity of discharge medium current-carrying is 1.8ml/min.The voltage of direct supply adopts 1100V, discharge current 60mA.Nitrogen is adopted in carrier gas, and flow velocity is 600ml/min.Liquid-phase chromatographic column is PRP X-200 post (250 * 4.1mm, 10 μ m), and moving phase is 3% (v/v) acetonitrile+1% (w/w) L-halfcystine+20mmol l
-1Pyrimidine+160mmol l
-1Formic acid, the flow velocity of moving phase are 1.0ml min
-1Detect three kinds of mercury signals in the shrimp sample with atomic fluorescence, signal is with the linear variation of different sample concentrations.
Claims (10)
1. mercury morphological analysis method based on liquid cathode discharge, it is characterized in that: the testing sample solution that will contain mercury is introduced in the chromatographic column of liquid chromatograph, the discharge medium current-carrying then is incorporated in the sample introduction kapillary in discharge pond by sampling device with the effluent of chromatographic column by threeway, with the metal electrode is anode, with graphite, platinum or stainless steel material are negative electrode, anode and sample introduction arcing distance capillaceous is 0.5mm～3.0mm, adopt direct supply, at discharge current is to carry out liquid cathode discharge generation steam under 20mA～90mA condition, the steam that makes discharge generation then enters under carrier gas drives and carries out gas-liquid separation in the gas-liquid separator, adopt atomic fluorescence spectrometer that isolated gas is carried out the fluoroscopic examination analysis, can draw the form of mercury; Described discharge medium is any or several potpourri in nitric acid, sulfuric acid or the phosphoric acid, and the pH value of discharge medium is 1.0～3.0.
2. the mercury morphological analysis method based on the liquid cathode discharge according to claim 1, it is characterized in that: described sampling device is a peristaltic pump.
3. the mercury morphological analysis method based on the liquid cathode discharge according to claim 1, it is characterized in that: the flow velocity of discharge medium current-carrying is 1.0ml/min～2.0ml/min, the voltage of direct supply is 500V～1200V, carrier gas is any or several mixed gas in air, nitrogen, helium, argon gas or the oxygen, flow rate of carrier gas is 200ml/min～800ml/min, gas-liquid separator is circumscribed with recirculated cooling water, and the temperature of chilled water is 0.1 ℃～5 ℃.
4. the mercury morphological analysis method based on liquid cathode discharge according to claim 1 is characterized in that: the material of described metal electrode is any or several alloy in platinum, tungsten or the titanium.
5. the mercury morphological analysis method based on the liquid cathode discharge according to claim 1, it is characterized in that: contain organic acid, alcohol, ketone or alkane in the discharge medium, this organic acid, alcohol, ketone or the alkane concentration of volume percent in discharge medium is 0.1%～2.0%.
6. the described used mercury vapour generating means of mercury morphological analysis method of a claim 1 based on the liquid cathode discharge, it is characterized in that: this device is airtight liquid cathode discharge pond, the upper and lower in discharge pond is respectively equipped with anode and negative electrode, circuit connects direct supply by two electrodes and constitutes, the bottom in discharge pond is provided with the sample introduction kapillary, it is relative with anode that a sample introduction end capillaceous is positioned at the discharge pond, its other end is positioned at discharge outside, pond, anode and sample introduction arcing distance capillaceous is 0.5mm～3.0mm, the side wall upper part in discharge pond is provided with gas vent, and its underpart is provided with carrier gas inlet and waste liquid outlet.
7. mercury vapour generating means according to claim 6 is characterized in that: anode is a metal electrode, and the material of metal electrode is any or several alloy in platinum, tungsten or the titanium, and the material of negative electrode is graphite, platinum or stainless steel.
8. mercury vapour generating means according to claim 6 is characterized in that: the voltage of direct supply is 500V～1200V.
9. mercury vapour generating means according to claim 6 is characterized in that: the porcelain tube resistance that is provided with a 1K Ω～5K Ω in the circuit.
10. mercury vapour generating means according to claim 6 is characterized in that: sample introduction internal diameter capillaceous is 0.1mm～0.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105203521A CN102033103A (en) | 2010-10-26 | 2010-10-26 | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105203521A CN102033103A (en) | 2010-10-26 | 2010-10-26 | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102033103A true CN102033103A (en) | 2011-04-27 |
Family
ID=43886275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105203521A Pending CN102033103A (en) | 2010-10-26 | 2010-10-26 | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102033103A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353799A (en) * | 2011-07-25 | 2012-02-15 | 中国地质大学（武汉） | Method of evaporating sample injecting inducted by dielectric barrier discharge microplasma |
| CN105004709A (en) * | 2015-04-13 | 2015-10-28 | 中国地质大学（武汉） | Liquid discharge micro-plasma excitation source apparatus and plasma excitation method |
| CN105092763A (en) * | 2015-08-26 | 2015-11-25 | 北京市理化分析测试中心 | Electrochemical pre-reduction method and device for mercury speciation analysis by HPLC-AFS (high performance liquid chromatography and atomic fluorescence spectroscopy) |
| CN105886796A (en) * | 2016-03-15 | 2016-08-24 | 中国华电集团科学技术研究总院有限公司 | Device for producing mercury standard gas and divalent mercury standard gas on basis of saturation principle |
| CN107894511A (en) * | 2017-10-27 | 2018-04-10 | 河北莱博瑞特电子科技有限公司 | A kind of Elemental Speciation Analysis instrument |
| CN108844927A (en) * | 2018-04-20 | 2018-11-20 | 中国地质大学（武汉） | A kind of sample introduction system and its Atomic Fluorescence Spectrometer |
| CN112630208A (en) * | 2019-10-09 | 2021-04-09 | 中国科学院上海硅酸盐研究所 | Sample introduction system for atomic spectrum or mass spectrum |
| CN112782150A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院上海硅酸盐研究所 | Sample introduction system for liquid cathode glow discharge spectrometer |
| US11133146B2 (en) | 2019-12-02 | 2021-09-28 | 2S Water Incorporated | Solution electrode glow discharge apparatus |
| US11150192B2 (en) | 2020-01-20 | 2021-10-19 | 2S Water Incorporated | Liquid electrode tip |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101236183A (en) * | 2008-02-04 | 2008-08-06 | 浙江大学 | Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system |
| CN101556246A (en) * | 2009-04-17 | 2009-10-14 | 中国地质大学（武汉） | Mercury vapour generation method and device |
-
2010
- 2010-10-26 CN CN2010105203521A patent/CN102033103A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101236183A (en) * | 2008-02-04 | 2008-08-06 | 浙江大学 | Ion chromatograph -double anode electrochemical hydride generation atomic fluorescent on-line combined system |
| CN101556246A (en) * | 2009-04-17 | 2009-10-14 | 中国地质大学（武汉） | Mercury vapour generation method and device |
Non-Patent Citations (1)
| Title |
|---|
| 《Analytical Chemistry》 20080915 zhenli zhu，et.al. Use of a Solution Cathode Glow Discharge for Cold Vapor Generation of Mercury with Determination by ICP-Atomic Emission Spectrometry , * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353799A (en) * | 2011-07-25 | 2012-02-15 | 中国地质大学（武汉） | Method of evaporating sample injecting inducted by dielectric barrier discharge microplasma |
| CN105004709A (en) * | 2015-04-13 | 2015-10-28 | 中国地质大学（武汉） | Liquid discharge micro-plasma excitation source apparatus and plasma excitation method |
| CN105092763A (en) * | 2015-08-26 | 2015-11-25 | 北京市理化分析测试中心 | Electrochemical pre-reduction method and device for mercury speciation analysis by HPLC-AFS (high performance liquid chromatography and atomic fluorescence spectroscopy) |
| CN105886796A (en) * | 2016-03-15 | 2016-08-24 | 中国华电集团科学技术研究总院有限公司 | Device for producing mercury standard gas and divalent mercury standard gas on basis of saturation principle |
| CN107894511A (en) * | 2017-10-27 | 2018-04-10 | 河北莱博瑞特电子科技有限公司 | A kind of Elemental Speciation Analysis instrument |
| CN107894511B (en) * | 2017-10-27 | 2023-09-15 | 河北莱博瑞特电子科技有限公司 | Elemental morphology analyzer |
| CN108844927A (en) * | 2018-04-20 | 2018-11-20 | 中国地质大学（武汉） | A kind of sample introduction system and its Atomic Fluorescence Spectrometer |
| CN112630208A (en) * | 2019-10-09 | 2021-04-09 | 中国科学院上海硅酸盐研究所 | Sample introduction system for atomic spectrum or mass spectrum |
| CN112782150A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院上海硅酸盐研究所 | Sample introduction system for liquid cathode glow discharge spectrometer |
| US11133146B2 (en) | 2019-12-02 | 2021-09-28 | 2S Water Incorporated | Solution electrode glow discharge apparatus |
| US11150192B2 (en) | 2020-01-20 | 2021-10-19 | 2S Water Incorporated | Liquid electrode tip |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102033103A (en) | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device | |
| Zou et al. | Recent trends in atomic fluorescence spectrometry towards miniaturized instrumentation-A review | |
| Jamroz et al. | Development of direct-current, atmospheric-pressure, glow discharges generated in contact with flowing electrolyte solutions for elemental analysis by optical emission spectrometry | |
| He et al. | Flowing and nonflowing liquid electrode discharge microplasma for metal ion detection by optical emission spectrometry | |
| Liu et al. | Plasma induced chemical vapor generation for atomic spectrometry: a review | |
| Liu et al. | Advances in discharge-based microplasmas for the analysis of trace species by atomic spectrometry | |
| US10705023B2 (en) | Solution cathode glow discharge plasma-atomic emission spectrum apparatus and method capable of performing direct gas sample introduction and used for detecting heavy metal element | |
| CN204154649U (en) | A kind of chromium Elemental Speciation Analysis device | |
| He et al. | Dielectric barrier discharge micro-plasma emission source for the determination of thimerosal in vaccines by photochemical vapor generation | |
| CN106568833B (en) | A kind of liquid cathode glow discharge optical emission spectrometry device and method for heavy metal analysis | |
| JPH09138218A (en) | Method and device for analyzing sample by flame | |
| Leng et al. | A sensitive and compact mercury analyzer by integrating dielectric barrier discharge induced cold vapor generation and optical emission spectrometry | |
| Li et al. | Atomic spectrometric detectors for gas chromatography | |
| Hu et al. | Current advances of chemical vapor generation in non-tetrahydroborate media for analytical atomic spectrometry | |
| Zhang et al. | Review of miniaturized and portable optical emission spectrometry based on microplasma for elemental analysis | |
| CN105004709A (en) | Liquid discharge micro-plasma excitation source apparatus and plasma excitation method | |
| CN102354649A (en) | Surface extraction chemical ionization source and surface extraction chemical ionization mass spectrometry method | |
| CN101556246A (en) | Mercury vapour generation method and device | |
| Liu et al. | Fast and highly sensitive Cd isotopic analyses in low-Cd complex samples with MC-ICPMS based on plasma electrochemical vapor generation | |
| Li et al. | Development of a new hybrid technique for rapid speciation analysis by directly interfacing a microfluidic chip‐based capillary electrophoresis system to atomic fluorescence spectrometry | |
| CN108844927B (en) | Sample introducing system and atomic fluorescence spectrometer thereof | |
| Gao et al. | Determination of mercury in alcoholic drinks by ICP-MS after matrix-assisted photochemical vapor generation | |
| He et al. | High-yield sample introduction using nebulized film dielectric barrier discharge assisted chelate vapor generation for trace rare earth elements determination by inductively coupled plasma mass spectrometry | |
| CN108489968A (en) | A kind of method of easy detection dithiocarbamates pesticide | |
| CN105092763A (en) | Electrochemical pre-reduction method and device for mercury speciation analysis by HPLC-AFS (high performance liquid chromatography and atomic fluorescence spectroscopy) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110427 |