CN103837632B - Device and method for measuring cadmium in water through liquid chromatogram flow injection chemiluminescence - Google Patents
Device and method for measuring cadmium in water through liquid chromatogram flow injection chemiluminescence Download PDFInfo
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- CN103837632B CN103837632B CN201410082138.0A CN201410082138A CN103837632B CN 103837632 B CN103837632 B CN 103837632B CN 201410082138 A CN201410082138 A CN 201410082138A CN 103837632 B CN103837632 B CN 103837632B
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Abstract
The invention provides a device and a method for measuring a cadmium element in water through liquid chromatogram flow injection chemiluminescence. According to the method, a complex is formed based on cadmium in the water and methyl glycol biacrylate, chemiluminescence is generated by the complex and ethyl acetoacetate in a cyclohexane organic phase system, a linear relationship exists between the chemiluminescence intensity and the concentration of the cadmium element in the water, and a method for measuring the cadmium in the water through the liquid chromatogram flow injection chemiluminescence is established by utilizing a liquid chromatographic separation flow injection technology. The method for measuring the cadmium element in the water has the characteristics of field measurement, rapidness, simplicity and sensitivity.
Description
Technical field
The present invention relates to environmental chemistry monitoring technical field, specifically relate to the method measuring Cadmium In The Water Body element.
Background technology
Cadmium In The Water Body is the problem that water body environment pollution one of facing is very important in recent years.In order to carry out evaluation and the improvement of science to the pollution level of Cadmium In The Water Body element, need to analyze the rapid determination of content of cadmium element in water body and valence state, form etc.The method of current mensuration Cadmium In The Water Body element mainly contains: colour developing spectrophotometric method, atomic absorption spectrography (AAS), atomic emission spectrometry, ICP-MS and electrochemical methods etc.The method duration is long, and analytic process is numerous and diverse, and condition is harsh, reagent consumption is large, and what have needs the poisonous organic extractant of employing and developer, produces secondary pollution.Majority method needs expensive large-scale instrument, method is all arrive the pattern of lab analysis after adopting on-site sampling in addition, namely the mode can not realize scene, measuring in real time, sample transportation and processing procedure easily introduce other interfering materials, the accuracy of impact analysis.Therefore this process is for trace level ultimate analysis, the possibility that there will not be secondary to get dirty in can not ensureing, and for ocean maternal environment complicated and changeable, such as: element morphology affects greatly by space-time; Majority is in again interrelated, interactional state; In environment, greatly, accuracy and the reliability of its result are under suspicion, thus can not definitely grasp seawater quality present situation and ANOMALOUS VARIATIONS thereof in temperature, pressure change.
In recent years, along with the development of electronic technology, new material, new technology, new optical device, especially computer technology is with rapid changepl. never-ending changes and improvements, the corresponding appearance of method of heavy metal in sea water element is analyzed by automatic analyzer, although these technology have broken away from some shortcomings of lab analysis, as the duration is long, analytic process is numerous and diverse, condition is harsh, but it also also exists, and poor stability, sensitivity and resolution are low, ion interference etc. is difficult to the defect overcome, make it range of application to be restricted, could not be widely used.
To there is extraction efficiency low for existing extracting process and device in addition, and layering is uneven, and organic solvent use amount is large, has the problem of secondary pollution.It is not high that the chromatography packed column of present use has separating power, the defect that dead volume is large.
Summary of the invention
The invention provides the device and method that a kind of liquid chromatogram mobile injected chemical luminescence method measures Cadmium In The Water Body, what it can solve that prior art exists can not work on the spot, and analyze the duration long, analytic process is numerous and diverse, condition is harsh, energy consumption is large, especially produces secondary pollution problems.By innovative design extraction cell and chromatography packed column, solving existing extracting process and device, to there is extraction efficiency low, and layering is uneven, and organic solvent use amount is large, has the problem of secondary pollution; Solving the chromatography packed column used now, to have separating power not high, and disengaging time is long, the defect that dead volume is large, achieves efficient extraction, quick separating Flow Injection Chemiluminescence measurement Cadmium In The Water Body element.
In order to reach the object solved the problems of the technologies described above, technical scheme of the present invention is, liquid chromatogram mobile injected chemical luminescence method measures the device of Cadmium In The Water Body, and described device comprises extraction cell, threeway sampling valve, chromatography packed column, sensing chamber, Electro-Optical Sensor Set, control device, data processing equipment, water sample pump, phosphoric acid pump, methacrylic acid diethylene glycol dilaurate pump, cyclohexane pump, organic phase pump, mobile phase high pressure pump, ethyl acetoacetate pump, extraction cell, threeway sampling valve, connected by pipeline between chromatography packed column and sensing chamber and aforesaid liquid, described extraction cell includes extraction upper strata from top to bottom successively, extraction turbulent area, extraction lower floor and air chamber, described extraction upper strata is interval with multiple tracks upper partition, described upper partition is made up of the material of 70%-80% methyl polysiloxane and 20%-30% polyglycol, described extraction lower floor is interval with multiple tracks lower partition, described lower partition is made up of the material of 20%-30% methyl polysiloxane and 70%-80% polyglycol, described air chamber is communicated with nitrogen, stainless steel microwell plate is provided with in the middle of described extraction lower floor and described air chamber, entry to mixed solution is provided with in described extraction lower floor, organic phase outlet is provided with on described extraction upper strata, described chromatography packed column two ends are provided with permanent magnet, and middle packed column is made up of filler and magnetic Nano material.
Described extraction upper strata and extraction lower floor cylindrical, extraction turbulent area is by reverse frustoconic and positive truncated cone-shaped is opposed is formed, and described air chamber is conically.
Described filler is carrier by corrosive acid sodium, immobile liquid is made up of cyanopropyl 30%, methyl-polysiloxane 50% and polyglycol 20%, described magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material wrapping up in polymethacrylate, and described filler and described magnetic Nano material proportional range are 10:(0.8-1.2).
Utilize above-mentioned liquid chromatogram mobile injected chemical luminescence method to measure a measuring method for the device of Cadmium In The Water Body, described method is carried out in the steps below by described device:
(1), luminous agent-ethyl acetoacetate under pumping action as current-carrying;
(2), water sample solution mixes with the phosphoric acid in phosphoric acid pipeline under the effect of water sample pump, ensures that water body system pH maintains 5.0-6.0;
(3), with the mixed mixed solution of phosphoric acid continue to flow in pipeline, then mix with the methacrylic acid diethylene glycol dilaurate in complexing agent-methacrylic acid diethylene glycol dilaurate pipeline, form methacrylic acid diethylene glycol dilaurate complex compound;
(4), mixed mixed solution continues to flow in pipeline, mix with the cyclohexane in cyclohexane pipeline again, together flow into extraction cell, nitrogen is passed into below extraction cell, bubbling 30-50s, static 30-50s again, solution layering, the organic phase that cyclohexane extraction methacrylic acid diethylene glycol dilaurate complex compound is formed is on extraction upper strata;
(5), organic phase is transported in the quantity tube of threeway sampling valve by organic phase pump;
(6) after, quantity tube is filled with sample, threeway sampling valve cuts out sample delivery channel, mobile phase-isopropyl alcohol carries sample and enters chromatography packed column by the quantity tube of threeway sampling valve under the effect of mobile phase high pressure pump, the Stationary liquid of sample and packed column interacts, distribute between mobile phase and Stationary liquid, because component each in sample is different from the affinity of Stationary liquid, therefore in sample, each component successively flows out chromatography packed column by it the different of two alternate affinity;
(7), from chromatography packed column flow out mix with current-carrying with the solution of separation component after together with to circulate sensing chamber, the chemiluminescence signal of retention time 7-9min component in the photomultiplier detection solution in Electro-Optical Sensor Set;
(8), photomultiplier carries out collection amplification to the light signal that the solution flowed through sends, and convert electric signal feeding microcomputer data processing equipment to, data processing equipment calculates the blank signal obtained and sample signal, again according to the signal suppressing degree difference data corresponding relation of signal suppressing degree difference data and standard model, calculate the concentration of each heavy metal element in seawater, and carry out showing, printout.
In the inventive solutions, the present invention also has following additional technical feature:
Described water sample liquid inventory is 5.0-10ml/min.
Described phosphoric acid flow is 0.1-0.5ml/min, and concentration is (1.0-1.5) × 10
-4mol/L.
Described methacrylic acid diethylene glycol dilaurate flow is 0.1-0.5ml/min, and concentration is (0.5-1.0) × 10
-2mol/L.
Described cyclohexane flow is 0.1-0.2ml/min.
The nitrogen flow that described bubbling enters the air chamber of extraction cell is 20-50ml/min.
Described ethyl acetoacetate is as current-carrying under pumping action, and flow is 0.5-1.0ml/min, and concentration is 0.1-0.3mol/L.
Described mobile phase-isopropyl alcohol flow is 0.1-0.3ml/min, and concentration is 0.01-0.03mol/L.
The extraction upper strata of extraction cell is provided with four layers of dividing plate, be made up of the material containing 75% methyl polysiloxane and 25% polyglycol, methyl polysiloxane lipophilicity, polyglycol water wettability, be conducive to organic phase like this and be separated floating, extraction lower floor is provided with four layers of dividing plate, be made up of the material containing 25% methyl polysiloxane and 75% polyglycol, be conducive to water sample separation like this to float downward, in the middle of extraction cell, extraction turbulent area is formed by two round platforms are opposed, form the structure of first shrinking further expansion from bottom to up, be beneficial to turbulization, be beneficial to separation, increase turbulence effect, improve effect of extracting.Dividing plate is uniformly distributed circular hole, ensures that liquid phase freely passes through.Be provided with stainless steel microwell plate in the middle of the extraction lower floor of extraction cell and air chamber, be evenly provided with micropore above, ensure that gas freely passes into, and liquid phase is non-leakage.
Described sensing chamber adopts stainless steel material.
Quantity tube volume scope in described threeway sampling valve is 10-15 μ L.
Described chromatography packed column two ends are provided with permanent magnet, ensure that whole packed column is in paramagnetic field.Liquid phase packed column is made up of filler and magnetic Nano material in addition, filler uses corrosive acid sodium to be carrier, immobile liquid is 30% cyanopropyl-50% methyl-polysiloxane-20% polyglycol composition, magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material wrapping up in polymethacrylate, and filler and magnetic Nano material ratio are 10:1., magnetic Nano material, under whole paramagnetic field action, produces micro-magnetic field, and micro-magnetic field effectively improves the thermodynamics and kinetics characteristic affecting post effect between liquid phase packed column Stationary liquid and mobile phase.Enhance the allocative efficiency between mobile phase and Stationary liquid, improve post effect, ensure that because component each in sample is different from the affinity of Stationary liquid, in sample, each component successively flows out chromatography packed column by it the different of two alternate affinity.
Described photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
Described high pressure pump is mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
Described method, utilizes microcomputer data processing equipment, realizes controlling described data processing equipment, the calculating of signal transacting and Cadmium In The Water Body concentration by software programming.
Cadmium In The Water Body forms complex compound with methacrylic acid diethylene glycol dilaurate under acid system, this reaction efficiency is high, fast, this complex compound produces chemiluminescence phenomenon with ethyl acetoacetate in cyclohexane organic phase simultaneously, and the concentration of chemiluminescence degree and Cadmium In The Water Body element has linear relationship.Because Cadmium In The Water Body element is formed in complex compound process with methacrylic acid diethylene glycol dilaurate under acid system, some organic by-products of easy generation, this accessory substance likely strengthens or suppresses the chemiluminescence phenomenon that methacrylic acid diethylene glycol dilaurate complex compound and ethyl acetoacetate produce, interference is brought to system, in order to eliminate the interference that accessory substance brings, adopt liquid chromatogram mobile injection system, special liquid phase packed column has selectivity, namely selectivity exchange is carried out to different structure organism, different according to separately from exchanger affinity, there is the characteristic that retention time is different, packed column adopts the filler containing magnetic Nano material in addition, the magnetic packed column of mating band, magnetic Nano material is under whole paramagnetic field action, produce micro-magnetic field, micro-magnetic field effectively improves the thermodynamics and kinetics characteristic affecting post effect between liquid phase packed column Stationary liquid and mobile phase, enhance the allocative efficiency between mobile phase and Stationary liquid, improve post effect, ensure that because component each in sample is different from the affinity of Stationary liquid, in sample, each component successively flows out chromatography packed column by it the different of two alternate affinity.Liquid chromatography has highly sensitive, and analysis speed is fast, is separated, applies widely so be obtained in many scientific domains such as environmental chemistry, Food Chemistry, chemical industry, electronics, biological medicine, new material research while realizing gas chromatography.Utilize in liquid chromatogram mobile injection technique quick separating complex reaction process and form multiple organism, detected the method for the liquid chromatogram mobile injected chemical luminescence method mensuration Cadmium In The Water Body element of the chemiluminescence degree foundation that object produces by retention time.Adopt the present invention to measure Cadmium In The Water Body element and there is scene, fast, easy, sensitive feature.
The integrated liquid chromatogram mobile injected chemical emitting photo detection system that the method that liquid chromatogram mobile injected chemical luminescence method measures Cadmium In The Water Body element is made up of light, mechanical, electrical, computing machine.Five parts can be divided into by operational module:
Part I: extractive reaction system, comprise: water sample pump, phosphoric acid solution pump, methacrylic acid diethylene glycol dilaurate solution pump, cyclohexane pump, extraction cell, form complex compound with methacrylic acid diethylene glycol dilaurate under the acid system that in water sample, cadmium element provides at phosphoric acid, then in extraction cell, utilize cyclohexane to extract form methacrylic acid diethylene glycol dilaurate and form complex compound in organic phase;
Part II: liquid chromatographic separation system, comprise: high pressure pump, mobile phase-isopropyl alcohol liquid reservoir, threeway sampling valve, liquid phase packed column, mobile phase-isopropyl alcohol carries sample and enters the long pig post in liquid phase sky by the quantity tube of threeway sampling valve under the effect of high pressure pump, the Stationary liquid of sample and packed column interacts, distribute between mobile phase and Stationary liquid, because component each in sample is different from the affinity of Stationary liquid, therefore in sample, each component successively flows out chromatography packed column by it the different of two alternate affinity;
Part III is flow injection part, mainly ethyl acetoacetate under pumping action as one moving, without the continuous current-carrying of airspace, this current-carrying mixes by carrier band in sensing chamber successively with the sample separated from liquid chromatography packed column.
Part IV: opto-electronic conversion and amplifier section, the main low-light photomultiplier that adopts is as detecting element, and carrier fluid circulation sensing chamber, the light signal of generation is transformed into electric signal immediately, and is continuously recorded.
Part V is data acquisition, recording section, and this part completes collection, A/D conversion, the transmission of electric signal and stores.
Part VI is microcomputer data handling system, primary responsibility calculates the blank signal obtained and sample signal, again according to the signal level data corresponding relation of signal level data and standard model, calculate the concentration of Cadmium In The Water Body element, and carry out showing, printout.
Because usual chemiluminescence reaction speed is very fast; so must ensure sample and luminescence reagent can fast, effectively, mixing of highly reappearing; liquid chromatography separated flow injection technique meets this requirement; therefore liquid chromatography separated flow injection technique combines with chemiluminescence analysis, and to measure the method for Cadmium In The Water Body element not only highly sensitive for the liquid chromatogram mobile injected chemical luminescence method that produces; the range of linearity is wide; and fast, favorable reproducibility, automaticity be high, can be developed rapidly in fields such as environmental analyses.
The present invention is the method measured by integrated abstraction technique, liquid chromatography isolation technics, Flow Injection Technique, chemiluminescence, electrooptical device, data acquisition, the carrying out of software process to Cadmium In The Water Body element.Method has scene, fast, easy, sensitive feature, what it can solve that prior art exists can not work on the spot, analyzes the duration long, analytic process is numerous and diverse, condition is harsh, energy consumption is large, and especially producing secondary pollution problems, is current very effective express-analysis means, be desirable environmental analysis detection method, belong to environmental protection method.The advantage that this method has can make this method be developed in fields such as environmental analyses and promote.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, method of the present invention is described in detail.
Fig. 1 is the inventive method principle of work process flow diagram;
Fig. 2 is the structure of the detecting device schematic diagram that the inventive method adopts.
1, mobile phase; 2, mobile phase high pressure pump; 3, threeway sampling valve; 4, organic phase pump; 5, extraction cell; 6, nitrogen cylinder; 7, chromatography packed column; 8, cyclohexane; 9., cyclohexane pump; 10, complexing agent; 11, complexing agent pump; 12, phosphoric acid; 13, phosphoric acid pump; 14, water sample; 15, blank solution; 16, water sample pump; 17, ethyl acetoacetate pump; 18, luminous agent; 19, sensing chamber; 20, control device; 21, data processing equipment; 22, liquid waste processing; 23, photodetecting part.
Fig. 3 is the extraction cell structural representation that the inventive method adopts.
5, extraction cell; 5-1, nitrogen atmospheric valve; 5-2, organic phase fluid export; 5-3, upper partition; 5-4, extraction turbulent area; 5-5, lower partition; 5-6, stainless steel microwell plate; 5-7, air chamber; 5-8, nitrogen inlet; 5-9, entry to mixed solution.
Fig. 4 is the liquid phase packed column structural representation that the inventive method adopts.
7, chromatography packed column; 7-1, mobile phase entrance; 7-2, packed column permanent magnet; 7-3, packed column; 7-4, packed column permanent magnet; 7-5, mobile phase export.
Embodiment
See Fig. 3, the structure of extraction cell 7 is divided into extraction upper strata, extraction turbulent area 5-4, extraction lower floor and air chamber 5-7 from the top down, extraction upper strata and extraction lower floor are cylindrical shape, and extraction turbulent area 5-4 is by reverse frustoconic and positive truncated cone-shaped is opposed is formed, and described air chamber 5-7 conically.Described extraction upper strata is interval with 4 unexposed layer dividing plate 5-3, described upper partition 5-3 is made up of the material of 75% methyl polysiloxane and 25% polyglycol, described extraction lower floor is interval with 4 road lower partition 5-5, described lower partition 5-5 is made up of the material of 25% methyl polysiloxane and 75% polyglycol, described air chamber 5-7 is communicated with nitrogen cylinder 6, see Fig. 2, stainless steel microwell plate 5-6 is provided with in the middle of described extraction lower floor and described air chamber 5-7, extraction lower floor on stainless steel microwell plate 5-6 is provided with entry to mixed solution 5-9, extraction upper strata body under first upper partition 5-3 is provided with organic phase outlet 5-2.
See Fig. 4, the two ends up and down of described chromatography packed column 7 are provided with permanent magnet 7-2,7-4, and middle packed column 7-3 is made up of filler and magnetic Nano material.Filler is carrier by corrosive acid sodium, immobile liquid is made up of cyanopropyl 30%, methyl-polysiloxane 50% and polyglycol 20%, described magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material wrapping up in polymethacrylate, and described filler and described magnetic Nano material proportional range are 10:1.Magnetic Nano material, under whole paramagnetic field action, produces micro-magnetic field, and micro-magnetic field effectively improves the thermodynamics and kinetics characteristic affecting post effect between liquid phase packed column Stationary liquid and mobile phase.Enhance the allocative efficiency between mobile phase and Stationary liquid, improve post effect, ensure that because component each in sample is different from the affinity of Stationary liquid, in sample, each component successively flows out chromatography packed column 7 by it the different of two alternate affinity.
See Fig. 1 and Fig. 2, a kind of liquid chromatogram mobile injected chemical luminescence method measures the device of Cadmium In The Water Body element, described device comprises extraction cell 5, threeway sampling valve 3, chromatography packed column 7, sensing chamber 19, Electro-Optical Sensor Set 23, control device 20, data processing equipment 21, water sample pump 16, phosphoric acid pump 12, methacrylic acid diethylene glycol dilaurate pump 11, cyclohexane pump 9, organic phase pump 4, mobile phase high pressure pump 2, ethyl acetoacetate pump 17, connected by pipeline between extraction cell 5, threeway sampling valve 3, chromatography packed column 7 and sensing chamber 19 and aforesaid liquid.
The method adopting apparatus of the present invention to measure Cadmium In The Water Body element comprises following step:
(1), luminous agent-ethyl acetoacetate 18 pump 17 act under as current-carrying;
(2), water sample solution mixes with the phosphatase 11 2 in phosphoric acid pipeline under the effect of water sample pump 16, ensures that water body system pH maintains 5.0-6.0;
(3), with the mixed mixed solution of phosphoric acid continue to flow in pipeline, then mix with the methacrylic acid diethylene glycol dilaurate 10 in complexing agent-methacrylic acid diethylene glycol dilaurate pipeline, form methacrylic acid diethylene glycol dilaurate complex compound;
(4), mixed mixed solution continues to flow in pipeline, mix with the cyclohexane 8 in cyclohexane pipeline again, together flow into extraction cell 5, extraction cell 5 passes into nitrogen by nitrogen cylinder 6 below, bubbling 30-50s, static 30-50 s again, solution layering, the organic phase that cyclohexane extraction methacrylic acid diethylene glycol dilaurate complex compound is formed is on extraction cell upper strata;
(5), organic phase pump 4 is transported to organic phase in the quantity tube of threeway sampling valve 3, and quantity tube volume is 10 μ L;
(6) after, the quantity tube of threeway sampling valve 3 is filled with sample, threeway sampling valve 3 cuts out sample delivery channel, mobile phase-isopropyl alcohol 1 carries sample and enters chromatography packed column 7 by the quantity tube of threeway sampling valve under the effect of mobile phase high pressure pump 2, the Stationary liquid of sample and chromatography packed column 7 interacts, distribute between mobile phase and Stationary liquid, because component each in sample is different from the affinity of Stationary liquid, therefore in sample, each component successively flows out chromatography packed column 7 by it the different of two alternate affinity;
(7), mix from chromatography packed column 7 solution flowed out with separation component with current-carrying after together with to circulate sensing chamber 19, the photomultiplier in Electro-Optical Sensor Set 23 detects the chemiluminescence signal of retention time 8min component in solution;
(8), photomultiplier carries out collection amplification to the light signal that the solution flowed through sends, and convert electric signal feeding microcomputer data processing equipment to, data processing equipment calculates the blank signal obtained and sample signal, again according to the signal suppressing degree difference data corresponding relation of signal suppressing degree difference data and standard model, calculate the concentration of each heavy metal element in seawater, and carry out showing, printout.
In the above-described embodiments:
Described water sample liquid inventory is 5.0-10ml/min.
Described phosphoric acid flow is 0.1-0.5ml/min, and concentration is (1.0-1.5) × 10
-4mol/L.
Described methacrylic acid diethylene glycol dilaurate flow is 0.1-0.5ml/min, and concentration is (0.5-1.0) × 10
-2mol/L.
Described cyclohexane flow is 0.1-0.2ml/min.
The nitrogen flow that described bubbling enters extraction cell is 20-50ml/min.
Described ethyl acetoacetate is as current-carrying under pumping action, and flow is 0.5-1.0ml/min, and concentration is 0.1-0.3mol/L.
Described mobile phase-isopropyl alcohol flow is 0.1-0.3ml/min, and concentration is 0.01-0.03mol/L.
Described sensing chamber 19 adopts stainless steel material to make.
Quantity tube volume scope in described threeway sampling valve 3 is 10-15 μ L, and the present embodiment quantity tube volume selects 10 μ L.
Described photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
Described high pressure pump is mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
Described method, is characterized in that utilizing microcomputer data processing equipment, realizes controlling described data processing equipment, the calculating of signal transacting and Cadmium In The Water Body concentration by software programming.
The above is only preferred embodiment of the present invention, and be not restriction the present invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.Allly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (10)
1. liquid chromatogram mobile injected chemical luminescence method measures a device for Cadmium In The Water Body, and described device comprises extraction cell, threeway sampling valve, chromatography packed column, sensing chamber, Electro-Optical Sensor Set, control device, data processing equipment, water sample pump, phosphoric acid pump, methacrylic acid diethylene glycol dilaurate pump, cyclohexane pump, organic phase pump, mobile phase high pressure pump, ethyl acetoacetate pump, extraction cell, threeway sampling valve, connected by pipeline between chromatography packed column and sensing chamber and said pump, it is characterized in that, described extraction cell includes extraction upper strata from top to bottom successively, extraction turbulent area, extraction lower floor and air chamber, described extraction upper strata is interval with multiple tracks upper partition, described upper partition is made up of the material of 70%-80% methyl polysiloxane and 20%-30% polyglycol, described extraction lower floor is interval with multiple tracks lower partition, described lower partition is made up of the material of 20%-30% methyl polysiloxane and 70%-80% polyglycol, described air chamber is communicated with nitrogen, stainless steel microwell plate is provided with in the middle of described extraction lower floor and described air chamber, entry to mixed solution is provided with in described extraction lower floor, organic phase outlet is provided with on described extraction upper strata, the two ends up and down of described chromatography packed column are provided with permanent magnet, and middle packed column is made up of filler and magnetic Nano material.
2. a kind of liquid chromatogram mobile injected chemical luminescence method according to claim 1 measures the device of Cadmium In The Water Body, it is characterized in that, described extraction upper strata and extraction lower floor cylindrical, extraction turbulent area is by reverse frustoconic and positive truncated cone-shaped is opposed is formed, and described air chamber is conically.
3. a kind of liquid chromatogram mobile injected chemical luminescence method according to claim 2 measures the device of Cadmium In The Water Body, it is characterized in that, described filler is carrier by corrosive acid sodium, immobile liquid is made up of cyanopropyl 30%, methyl-polysiloxane 50% and polyglycol 20%, described magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material wrapping up in polymethacrylate, and described filler and described magnetic Nano material proportional range are 10:(0.8-1.2).
4. utilize a kind of liquid chromatogram mobile injected chemical luminescence method described in claim 1 or 2 or 3 to measure a measuring method for the device of Cadmium In The Water Body, it is characterized in that, described method is carried out in the steps below by described device:
(1), luminous agent-ethyl acetoacetate under pumping action as current-carrying;
(2), water sample solution mixes with the phosphoric acid in phosphoric acid pipeline under the effect of water sample pump, ensures that water body system pH maintains 5.0-6.0;
(3), with the mixed mixed solution of phosphoric acid continue to flow in pipeline, then mix with the methacrylic acid diethylene glycol dilaurate in complexing agent-methacrylic acid diethylene glycol dilaurate pipeline, form methacrylic acid diethylene glycol dilaurate complex compound;
(4), mixed mixed solution continues to flow in pipeline, mix with the cyclohexane in cyclohexane pipeline again, together flow into extraction cell, nitrogen is passed into below extraction cell, bubbling 30-50s, static 30-50s again, solution layering, the organic phase that cyclohexane extraction methacrylic acid diethylene glycol dilaurate complex compound is formed is on extraction upper strata;
(5), organic phase is transported in the quantity tube of threeway sampling valve by organic phase pump;
(6) after, quantity tube is filled with sample, threeway sampling valve cuts out sample delivery channel, mobile phase-isopropyl alcohol carries sample and enters chromatography packed column by the quantity tube of threeway sampling valve under the effect of mobile phase high pressure pump, the Stationary liquid of sample and chromatography packed column interacts, distribute between mobile phase and Stationary liquid, because component each in sample is different from the affinity of Stationary liquid, therefore in sample, each component successively flows out chromatography packed column by it the different of two alternate affinity;
(7), from chromatography packed column flow out mix with current-carrying with the solution of separation component after together with to circulate sensing chamber, the chemiluminescence signal of retention time 7-9min component in the photomultiplier detection solution in Electro-Optical Sensor Set;
(8), photomultiplier carries out collection amplification to the light signal that the solution flowed through sends, and convert electric signal feeding microcomputer data processing equipment to, data processing equipment calculates the blank signal obtained and sample signal, again according to the signal suppressing degree difference data corresponding relation of signal suppressing degree difference data and standard model, calculate the concentration of cadmium in seawater element, and carry out showing, printout.
5. method according to claim 4, is characterized in that, described water sample liquid inventory is 5.0-10ml/min; Described phosphoric acid flow is 0.1-0.5ml/min, and concentration is (1.0-1.5) × 10
-4mol/L; Described methacrylic acid diethylene glycol dilaurate flow is 0.1-0.5ml/min, and concentration is (0.5-1.0) × 10
-2mol/L.
6. method according to claim 4, is characterized in that, described cyclohexane flow is 0.1-0.2ml/min.
7. method according to claim 4, is characterized in that, the nitrogen flow that described bubbling enters the air chamber of extraction cell is 20-50ml/min.
8. method according to claim 4, is characterized in that, described ethyl acetoacetate flow is 0.5-1.0ml/min, and concentration is 0.1-0.3mol/L.
9. method according to claim 4, is characterized in that, described mobile phase-isopropyl alcohol flow is 0.1-0.3ml/min, and concentration is 0.01-0.03mol/L.
10. method according to claim 4, is characterized in that, the quantity tube volume scope in described threeway sampling valve is 15-25 μ L.
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