CN108627497B - Mercury element morphological analysis method - Google Patents
Mercury element morphological analysis method Download PDFInfo
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- CN108627497B CN108627497B CN201710172178.8A CN201710172178A CN108627497B CN 108627497 B CN108627497 B CN 108627497B CN 201710172178 A CN201710172178 A CN 201710172178A CN 108627497 B CN108627497 B CN 108627497B
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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
- G01N21/62—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
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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
- G01N21/62—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
Abstract
The invention provides a simple, convenient and quick method for analyzing the form of mercury element with small volume and low power, which comprises the following steps: transporting the mixed solution of the sample and the low-molecular organic acid to a photochemical steam selective generator by a flow injection instrument; generating mercury vapor from the photochemical vapor-selective generator; the mercury vapor is transported to a liquid cathode glow discharge spectrometer for excitation and detection by means of a carrier gas controlled by a gas flow controller.
Description
Technical Field
The invention belongs to the field of atomic spectrum analysis, relates to a mercury element morphological analysis method, and particularly relates to a photochemical vapor generation-liquid cathode glow discharge spectral analysis method.
Background
The mercury element is widely distributed in nature, has high toxicity, is easy to enrich and remain in the environment and is difficult to degrade, and the mercury in the water environment is absorbed by passive plants and enriched and amplified through a food chain, thereby forming a great threat to the health and even life safety of human beings. The chemical morphology analysis of mercury is of increasing interest because its toxicity is closely related to its chemical morphology in the environment. Mercury mainly exists in the environment in the modes of element mercury, inorganic mercury and organic mercury, the inorganic mercury has two forms of univalent mercury and bivalent mercury, and univalent mercury is almost insoluble in water and unstable in the environment and is easily converted into element mercury and bivalent mercury; the organic mercury mainly comprises methyl mercury, ethyl mercury, phenyl mercury and the like. Organic mercury is much more toxic than elemental mercury and inorganic mercury, and methyl mercury is the most toxic organic mercury, readily penetrating biofilms and accumulating through the food chain. Methylmercury once brings great harm to human environmental health, and among the famous eight public nuisance events, the water guarantee event in Japan is caused by people eating marine products polluted by methylmercury. The content of the methyl mercury in aquatic animals and carnivorous fishes is limited in GB 2762-2012 'pollutant limit in food' in China, and the methyl mercury in the aquatic products (except the carnivorous fishes) is limitedThe limit index is 0.5 mg/kg-1The limit index of methylmercury of carnivorous fish (such as shark, tuna and other) is 1 mg/kg-1(fresh weight).
At present, the detection technology of mercury element morphological analysis mainly adopts a combined technology of a high-selectivity chromatographic separation system and a high-sensitivity atomic spectrum/mass spectrum detector to realize the on-line separation and determination of different forms of elements in a sample. The coupling technology mainly comprises high performance liquid chromatography-atomic absorption spectroscopy (HPLC-AAS), high performance liquid chromatography-atomic fluorescence spectroscopy (HPLC-AFS), high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), gas chromatography-mass spectrometry (GC-MS) and the like. However, the chromatographic separation system has complex device, high price, high operation cost, high power of the atomic spectrum/mass spectrum detector, high operation cost and high consumption of a large amount of inert and even dangerous gases, and is difficult to be used for field analysis and detection. Therefore, it is very important to develop a simple, convenient, fast, small-volume, low-power non-chromatographic separation technology and a micro-plasma in vitro atomic spectrum combined technology for element morphological analysis.
Photochemical Vapor Generation (PVG) is a recently rapidly developed sample introduction technique that uses stable low molecular organic acids, produces low amounts of hydrogen, is environmentally friendly, and can tolerate high concentrations of transition metal ions. PVG can not only reduce metal cations to zero valence or lowest valence state, but also convert organic form into inorganic form, so that it can be used as a gas sampling technique, and also can be used as a non-chromatographic separation technique in element form analysis. The non-chromatographic separation technology of PVG as different form compounds utilizes the difference in the ability of different forms of the same element to produce volatile matter under the radiation of an ultraviolet lamp under different selected conditions to realize the quantitative separation of two different forms of matter. Therefore, the PVG has very wide application prospect in simple, convenient, quick and low-cost non-chromatographic element morphological analysis. Liquid cathode glow discharge spectroscopy (SCGD-AES) is a microplasma atomic spectrum, has the advantages of stability of spectral measurement, no need of an atomizer and compressed gas, operation under atmospheric pressure, small volume, low power consumption, easiness in miniaturization and field analysis and the like, and is concerned in emerging atomic spectrum analysis.
Disclosure of Invention
In order to overcome the defects of complex device, large volume and high power in the existing mercury element morphological analysis method, the invention provides an analysis method which is simple, convenient and quick, and applies photochemical vapor selective generation-miniaturized liquid cathode glow discharge spectroscopy (PVG-SCGD-AES) with small volume and low power to mercury element morphological analysis.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: transporting the mixed solution of the sample and the low-molecular organic acid to a photochemical steam selective generator by a flow injection instrument; generating mercury vapor from the photochemical vapor-selective generator; the mercury vapor is transported to a miniaturized liquid cathode glow discharge spectrum for excitation and detection by means of a carrier gas controlled by a gas flow controller.
Preferably, an ultraviolet lamp with the wavelength of 185-365 nm is adopted in the photochemical steam selective generator.
Preferably, an ultraviolet lamp with power of 4-50W is adopted in the photochemical steam selective generator.
Preferably, the irradiation time of the ultraviolet lamp in the photochemical steam selective generator is 5-100 s.
And the wavelength, power and radiation time of the ultraviolet lamp can be changed, so that mercury in different forms can be effectively separated.
Preferably, the mercury vapor generated by the photochemical vapor selective generator is measured by the liquid cathode glow discharge spectrometer for a plurality of times, so as to calculate the content of mercury with different forms.
The photochemical vapor selective generation-miniaturized liquid cathode glow discharge spectral analysis method for mercury morphological analysis has the beneficial effects that:
(1) the method adopts a flow injection-photochemical vapor selective generation sampling technology to selectively generate different forms of mercury elements, and realizes effective separation of the mercury with different forms.
(2) The special device used in the method does not need chromatographic separation technologies such as HPLC and GC and the like, and is combined with the miniaturized liquid cathode glow discharge spectrum operated under atmospheric pressure, so the method is a simple, convenient and quick mercury element morphological analysis method.
Drawings
FIG. 1 is a schematic structural diagram of a photochemical vapor selective generation-miniaturized liquid cathode glow discharge spectroscopic analysis apparatus according to an embodiment of the present invention;
FIG. 2 is a graph showing the signal response of inorganic mercury and methylmercury at different irradiation times of 8W/254nm using the method of the present invention;
FIG. 3 is a graph showing the signal response of inorganic mercury and methylmercury at different irradiation times of 4W/365nm using the method of the present invention;
FIG. 4 is a mercury morphometric analysis technique scheme when using the method of the present invention;
reference numerals:
1 flow injection peristaltic pump;
1A peristaltic pump
1B peristaltic pump
2 a six-way valve;
3 a photochemical vapour selective generator;
4, mixing the sample with low molecular organic acid;
5, an ultraviolet lamp;
6, a spiral reaction tube;
7 gas-liquid separator;
8 a gas flow controller;
9, carrying a gas;
10 current limiting resistor;
11 hollow titanium tube anode;
12 a graphite electrode;
13 cathode glass capillary;
14 a glass tube;
15, waste liquid;
16 electrolyte solution;
17 a common peristaltic pump;
18 a liquid pool;
19 a conveying pipe;
20 a condenser lens;
21 an optical fiber;
22 a micro spectrometer;
23 computer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and embodiments, it being understood that the following embodiments are illustrative of the invention only and are not limiting.
Fig. 1 is a schematic structural diagram of a photochemical vapor selective generation-miniaturized liquid cathode glow discharge spectroscopy combined analysis apparatus for mercury morphological analysis according to an embodiment of the present invention.
The photochemical vapor selective generation-miniaturized liquid cathode glow discharge spectrum analysis device adopted by the method for analyzing the mercury element form comprises: a flow injector, a photochemical steam selective generator 3, a gas-liquid separator 7, a gas flow controller 8, a miniaturized liquid cathode glow discharge spectrometer and the like.
The flow injector transports the mixed solution of the sample and the low molecular organic acid to the photochemical vapor selective generator 3; the photochemical vapor selective generator 3 generates mercury vapor, and after gas-liquid separation, the mercury vapor is transported to a miniaturized liquid cathode glow discharge spectrum for excitation and detection through carrier gas controlled by a gas flow controller 8.
As shown in fig. 1, the flow injection apparatus in the analysis device comprises two peristaltic pumps 1A, 1B and a six-way valve 2; the photochemical steam selective generator 3 is composed of an ultraviolet lamp 5 and a spiral reaction tube 6. In a specific application, one peristaltic pump in the flow injection instrument transports a mixed solution 4 of a sample and low-molecular organic acid to a photochemical steam selective generator 3, the other peristaltic pump transports a carrier gas, and mercury steam generated by the photochemical steam selective generator 3 is transported to the gas-liquid separator 7 for gas-liquid separation; the six-way valve 2 controls the sequence of the mixed solution and carrier gas entering the photochemical vapor selectivity generator 3.
More specifically, in an embodiment of the analyzer, the photochemical vapor selective generator unit adopts a flow injection mode, and includes: the device comprises a flow injection instrument comprising a peristaltic pump 1A, a peristaltic pump 1B and a six-way valve 2, a photochemical steam selective generator 3, a gas-liquid separator 7 and a gas-flow controller 8. A peristaltic pump 1A in the flow injection instrument transports a mixed solution 4 of a sample and a low-molecular organic acid to a photochemical vapor selective generator 3; the peristaltic pump 1B transports a carrier gas 9, and transports the heavy metal element volatile matter to be detected generated by the photochemical steam selective generator 3 to a gas-liquid separator 7 for gas-liquid separation; the six-way valve 2 controls the sequence of the mixed solution 4 of the sample and the low molecular organic acid and the carrier gas 9 entering the photochemical vapor selective generator 3. Wherein the low molecular organic acid is formic acid, acetic acid or other low molecular organic acids. The low molecular organic acid is preferably 5-60% (V/V) formic acid. The carrier gas is argon, helium or other inert gases with the concentration of 60-120 mL/min.
The photochemical steam selective generator 3 is composed of a spiral reaction tube 6 which is formed by processing an ultraviolet lamp 5 and a quartz reaction tube. The inner diameter of the quartz reaction tube is 1.5-2.5 mm, and the outer diameter is 2.5-3.5 mm; the inner diameter of the spiral reaction tube 6 is 20-40 mm; the ultraviolet lamp 5 is placed in the spiral reaction tube 6.
The generation of the mercury element photochemical vapor requires a certain radiation time, and the mercury vapor generated by mercury in different forms has different efficiencies under radiation of different ultraviolet light energy and intensity. The efficiency of the photochemical vapor selective generator for generating mercury vapor is related to the energy, intensity and time of ultraviolet lamp radiation, the efficiency of different forms of mercury for generating mercury vapor requires different energy, intensity and time of ultraviolet lamp radiation, and the wavelength and power of the ultraviolet lamp radiation reflect the energy and intensity of the ultraviolet light. The ultraviolet lamp irradiation time is realized by changing different residence times of a peristaltic pump in the flow injection instrument. For example, the UV irradiation time is controlled by peristaltic pumps 1A and 1B in the flow injection apparatus. The peristaltic pumps 1A and 1B stop rotating for the ultraviolet irradiation time. The different ultraviolet light energy and intensity are realized by changing ultraviolet lamps with different wavelengths and power. Preferably, the wavelength of the ultraviolet lamp is 185-365 nm, and the power is 4-50W; the radiation time is 5-100 s. For example, the UV lamp 5 may be 4W/254nm, 8W/254nm, 16W/254nm, 4W/365nm, 8W/365nm, 15W/365 nm.
The middle of the gas-liquid separator and the miniaturized liquid cathode glow discharge spectrum comprises a transmission pipe 19 which is connected between the top end of a hollow titanium tube anode 11 in the miniaturized liquid cathode glow discharge spectrometer unit and an upper interface of a gas-liquid separator 7 of the photochemical steam generator, the inner diameter of the transmission pipe is 2.5-3.5 mm, and the outer diameter of the transmission pipe is 3.5-4.5 mm. Namely, the mercury vapor passing through the gas-liquid separator is transported to the miniaturized liquid cathode glow discharge spectrum through a transmission pipe for excitation.
In the analysis device, the miniaturized liquid cathode glow discharge spectrometer unit comprises an excitation system, a light splitting and detecting system and a data processing system. The excitation system comprises a common peristaltic pump 17, a sample inlet pipe, a liquid discharge pipe, a current limiting resistor 10, a graphite electrode 12, a hollow titanium tube anode 11, a liquid pool 18, a cathode glass capillary tube 13, a glass tube 14 and a three-dimensional platform, the light splitting and detecting system comprises a condensing lens 20, the three-dimensional platform, an optical fiber 21 and a micro spectrometer 22, and the data processing system comprises a computer provided with Spectrasuite software.
The working principle of the excitation and detection of the miniaturized liquid cathode glow discharge spectrum is as follows: the method comprises the steps of taking an electrolyte solution as a cathode, taking a hollow titanium tube as an anode, applying high voltage to the two electrodes to generate glow discharge micro-plasma between the two electrodes, transporting mercury vapor generated by a photochemical vapor selective generator into the glow discharge micro-plasma through carrier gas to excite, taking an optical fiber as a signal coupling device, and coupling measured light focused by a lens into a micro spectrometer for detection.
Specifically, the miniaturized liquid cathode glow discharge spectrometer unit takes a small-volume electrolyte solution 16 as a cathode and a hollow titanium tube with small-flow carrier gas introduced therein as an anode, and generates glow discharge micro-plasma between the two electrodes after applying high voltage to the two electrodes; the photochemical steam generator unit is formed into a structure which enables a sample to be detected to generate heavy metal element volatile matters to be detected and separates gas from liquid, the volatile matters to be detected of the metal elements to be detected generated by the photochemical steam generator unit enter a hollow titanium tube anode 11 in the miniaturized liquid cathode glow discharge spectrometer unit through a coupling instrument interface unit by means of carrier gas, the volatile matters to be detected are led to the glow discharge micro-plasma from the hollow titanium tube anode 11 and are excited to generate a characteristic emission spectrum, and finally the detection is carried out by a micro spectrometer 22.
Specifically, in the miniaturized liquid cathode glow discharge spectrometer unit of the present invention, the excitation system is formed as follows: a lead led out from the anode of the high-voltage power supply is connected with the anode 11 of the hollow titanium tube, and a lead led out from the cathode is connected with the graphite electrode 12 through the buffer resistor 10; the graphite electrode 12 horizontally penetrates through the wall of the liquid pool 18 and is fixed on one side of the liquid pool 18; the liquid pool 18 is positioned right below the hollow titanium tube anode 11; the cathode glass capillary 13 vertically penetrates through the porous graphite electrode 12 and the bottom of the liquid pool 18 and is positioned 3-4 mm under the hollow titanium tube anode 11; the glass tube 14 passes vertically through the bottom of the liquid pool 18; the hollow titanium tube anode 11 and the liquid pool 18 are fixed on a three-dimensional platform with the adjustable precision of 2 mu m in the direction X, Y, Z.
Preferably, the high-voltage power supply can adopt an HSPY-600 high-voltage source which has a rated current of 0.1A and can provide a high direct-current voltage of 0-2000V; the liquid bath 18 may be fabricated from an acid-resistant, corrosion-resistant, dielectric material such as polytetrafluoroethylene; the hollow titanium tube anode 11 can have an inner diameter of 0.8-1.2 mm and an outer diameter of 1.5-2.5 mm; the cathode glass capillary 13 may have an inner diameter of 0.38 mm and an outer diameter of 1.1 mm.
That is, preferably, the electrolyte solution continuously overflows from the top end of the cathode glass capillary 13 with an inner diameter of 0.38 mm and an outer diameter of 1.1 mm and contacts with the graphite electrode to serve as a discharge cathode; and introducing carrier gas into the hollow titanium tube with the inner diameter of 0.8-1.2 mm and the outer diameter of 1.5-2.5 mm, taking the hollow titanium tube as a discharge anode, applying high voltage to the two electrodes, and generating glow discharge micro-plasma between the two electrodes, wherein the glow discharge area is an area which is 3-4 mm between the two vertically placed electrodes.
The ignition of the experimental device needs inorganic acid with a certain concentration as electrolyte solution, and the electrolyte solution is preferably nitric acid and hydrochloric acid with the pH = 0.8-1.2. The electrolyte solution 16 is introduced into the cathode glass capillary 13 through a sample inlet pipe by a common peristaltic pump 17, and the waste liquid 15 in the liquid pool 18 is led out through a waste liquid pipe by the same common peristaltic pump 17.
The electrolyte solution 16 may be one of inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid having a pH of 0.8 to 1.2. During the experiment, the flow rate of the common peristaltic pump 17 can be adjusted to be 1.6-2.4 mL/min, so that the electrolyte solution 16 continuously overflows from the top end of the cathode glass capillary 13 of the miniaturized liquid cathode glow discharge spectrometer.
Preferably, the electrolyte solution is nitric acid or hydrochloric acid with pH = 0.8-1.2; the high-voltage power supply is HSPY-600 with rated current of 0.1A and direct-current high voltage of 0-2000V; the carrier gas is inert gas such as argon or helium.
The distance between the top end of the cathode glass capillary 13 and the bottom end of the hollow titanium tube anode 11 is kept to be 3-4 mm, and the electrolyte solution 16 overflowing from the top end of the cathode glass capillary 13 is in contact with the graphite electrode 12, so that a glow discharge loop is formed. After applying a high voltage to the two electrodes under atmospheric pressure, glow discharge microplasma is generated between the two electrodes. The hollow titanium tube anode 11 is also used as a gas pipeline, and the carrier gas brings the sample gas into the hollow titanium tube anode 11. In addition, the carrier gas is preferably an inert gas, which also has a function of cooling the hollow titanium tube anode 11 as a discharge gas to prevent the anode from being damaged by overheating.
In the miniaturized liquid cathode glow discharge spectrometer unit, the light splitting and detecting system forms the following structure: the condenser lens 20 is fixed on the adjustable bracket; the probe of the optical fiber 21 is fixed on a three-dimensional platform with the adjustable precision of 2 mu m in the direction X, Y, Z; the optical fiber 21 is used as a signal coupling device, couples the light focused by the condenser lens 20 into an entrance slit of the micro spectrometer 22, and is detected and amplified by a charge-coupled detector of the micro spectrometer 22; the center of the glow discharge region, the center of the condenser lens 20, and the center of the probe of the optical fiber 21 are located on the same straight line. The distance from the center of the lens to the center of the optical fiber probe is 5-10 cm, and the distance from the center of the glow discharge area to the center of the lens is 8-15 cm. Preferably, the distance from the center of the lens to the center of the optical fiber probe is 6.5 cm, and the distance from the center of the glow discharge area to the center of the lens is 10 cm.
The invention adopts a micro spectrometer model of Maya 2000, the micro spectrometer 22 is used for detection and amplification by a charge coupled detector, and finally the micro spectrometer is processed and displayed by computer Spectrasuite software. And obtaining the spectral intensity of each element, and then carrying out quantitative analysis by adopting the peak height so as to realize the detection of the heavy metal elements in the solution.
By adopting a flow injection-photochemical vapor selective generation sampling technology, under the radiation of an ultraviolet lamp with the wavelength of 185-365 nm, the power of 4-50W and the radiation time of 5-100 s, mercury vapor can be generated from inorganic mercury ions, organic mercury and other mercury in different forms, and signals are detected by a miniaturized liquid cathode glow discharge spectrum; under the radiation of an ultraviolet lamp with the wavelength of 364 nm, the power of 4W and the radiation time of less than 20 s, only inorganic mercury can be radiated by the ultraviolet light to generate mercury vapor, and signals are detected by a miniaturized liquid cathode glow discharge spectrum. Therefore, different forms of mercury elements selectively occur by changing the wavelength, power and radiation time of the ultraviolet lamp, then the content of organic mercury is obtained by multiple times of measurement through the miniaturized liquid cathode glow discharge spectrum, and finally the effective separation and detection of mercury with different forms are realized by using a subtraction method. The concrete description is as follows.
FIG. 2 is a graph showing the signal response of inorganic mercury and methylmercury at different irradiation times of 8W/254nm using the method of the present invention. FIG. 3 is a graph showing the signal response of inorganic mercury and methylmercury at different irradiation times of 4W/365nm when the method of the present invention is used. FIG. 4 is a mercury morphometric technical scheme when using the method of the present invention.
From fig. 2-4, a photochemical vapor selective generation-miniaturized liquid cathode glow discharge spectroscopic analysis method for mercury morphological analysis can be obtained. As shown in FIG. 2, when the ultraviolet lamp disposed in the photochemical vapor selective generator is 8W/254nm, the low-molecular organic acid is 20% (V/V) formic acid, and the flow rate of the carrier gas is 100 mL/min, 100 mug/L Hg and MeHg solution can generate mercury vapor within the radiation time of 10-80 s, and the signal is detected by the miniaturized liquid cathode glow discharge spectrum. As shown in FIG. 3, the ultraviolet lamp disposed in the photochemical vapor selective generator is 4W/365nm, the low-molecular organic acid is 20% (V/V) formic acid, and when the flow rate of the carrier gas is 100 mL/min, 100 mug/L Hg and MeHg solution can generate mercury vapor within 20-80 s of radiation time, and a signal is detected by the miniaturized liquid cathode glow discharge spectrum, but when the radiation time is less than 20 s, only Hg can be induced to generate mercury vapor, and a signal is detected by the miniaturized liquid cathode glow discharge spectrum. As shown in fig. 4, the flow injection-photochemical vapor-selective generation and sampling technology is adopted to selectively generate different forms of mercury elements, so that the effective separation of different forms of mercury is realized, and the method can be used together with the miniaturized liquid cathode glow discharge spectrum operated under the atmospheric pressure. The method is simple, convenient, rapid, small in volume and low in power, and the method is developed by changing the wavelength, power and radiation time of an ultraviolet lamp, then carrying out multiple times of measurement and finally obtaining the content of organic mercury by using a subtraction method.
The mercury morphological analysis method provided by the invention does not need to adopt a chromatographic separation system with complex device, high price and high operation cost, does not need to adopt an atomic spectrum/mass spectrum detector with high power, large volume and high cost, but adopts a flow injection-photochemical steam-selective generation sample injection technology to selectively generate different forms of mercury elements, realizes effective separation of the mercury with different forms, is used together with a miniaturized liquid cathode glow discharge spectrum operated under atmospheric pressure for excitation and detection, and develops a method for applying a non-chromatographic separation technology with simplicity, rapidness, small volume and low power and a micro-plasma atomic spectrum combined technology to mercury morphological analysis.
As the present invention may be embodied in several forms without departing from the spirit of essential characteristics thereof, the present embodiments are therefore illustrative and not restrictive, since the scope of the invention is defined by the appended claims rather than by the description herein, and all changes that fall within metes and bounds of the claims, or equivalence of such metes and bounds thereof are therefore intended to be embraced by the appended claims.
Claims (5)
1. The mercury element morphological analysis method is characterized by comprising the following steps:
transporting the mixed solution of the sample and the low-molecular organic acid to a photochemical steam selective generator by a flow injection instrument;
in the photochemical vapor selective generator, under the radiation of an ultraviolet lamp with the wavelength of 185-365 nm, the power of 8-50W and the radiation time of 5-100 s, mercury in different forms including inorganic mercury ions and organic mercury generates total mercury vapor as first mercury vapor; transporting the first mercury vapor to a liquid cathode glow discharge spectrometer for excitation and detection by means of a carrier gas controlled by a gas flow controller; and
in the photochemical steam selective generator, under the radiation of an ultraviolet lamp with the wavelength of 365nm, the power of 4W and the radiation time of 5-20 s, inorganic mercury ions generate second mercury steam; transporting the second mercury vapor to a liquid cathode glow discharge spectrometer for excitation and detection by means of a carrier gas controlled by a gas flow controller;
and calculating the content of mercury in different forms.
2. The analytical method according to claim 1,
generating the first mercury vapor in the photochemical vapor selective generator using an ultraviolet lamp having a wavelength of 254nm and a power of 8W.
3. The analytical method according to claim 1,
and generating the first mercury vapor in the photochemical vapor selective generator for an irradiation time of 20-80 s.
4. The analytical method according to claim 1,
the wavelength, power and radiation time of the ultraviolet lamp are changed, so that mercury in different forms can be effectively separated.
5. The analytical method according to claim 1,
the content of organic mercury is obtained by using a difference subtraction method.
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| CN101158667A (en) * | 2007-11-19 | 2008-04-09 | 中国科学院生态环境研究中心 | Method and equipment for separating and detecting organo-mercuric compound content |
| CN201096757Y (en) * | 2007-10-12 | 2008-08-06 | 中国科学院生态环境研究中心 | A device for measuring Hg content in biological and environmental sample |
| CN104237178A (en) * | 2014-10-09 | 2014-12-24 | 重庆邮电大学 | Method and device for detecting trace metal elements in water body by using laser-induced breakdown spectroscopy assisted by direct current discharging vaporization |
| CN105842230A (en) * | 2016-03-29 | 2016-08-10 | 中国科学院上海硅酸盐研究所 | Device and method for the detection of heavy metal elements |
| CN106568833A (en) * | 2016-10-11 | 2017-04-19 | 中国科学院上海硅酸盐研究所 | Photochemical steam generator and liquid cathode glow discharge spectrometer coupled analysis apparatus and method for detecting heavy metal by using apparatus |
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| EP3045895A1 (en) * | 2015-01-13 | 2016-07-20 | ARKRAY, Inc. | Plasma spectrochemical analysis method and plasma spectrochemical analyzer |
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| CN201096757Y (en) * | 2007-10-12 | 2008-08-06 | 中国科学院生态环境研究中心 | A device for measuring Hg content in biological and environmental sample |
| CN101158667A (en) * | 2007-11-19 | 2008-04-09 | 中国科学院生态环境研究中心 | Method and equipment for separating and detecting organo-mercuric compound content |
| CN104237178A (en) * | 2014-10-09 | 2014-12-24 | 重庆邮电大学 | Method and device for detecting trace metal elements in water body by using laser-induced breakdown spectroscopy assisted by direct current discharging vaporization |
| CN105842230A (en) * | 2016-03-29 | 2016-08-10 | 中国科学院上海硅酸盐研究所 | Device and method for the detection of heavy metal elements |
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