CN103837632A - 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
- Publication number
- CN103837632A CN103837632A CN201410082138.0A CN201410082138A CN103837632A CN 103837632 A CN103837632 A CN 103837632A CN 201410082138 A CN201410082138 A CN 201410082138A CN 103837632 A CN103837632 A CN 103837632A
- Authority
- CN
- China
- Prior art keywords
- extraction
- sample
- pump
- flow
- cadmium
- 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.)
- Granted
Links
Images
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 measure the method for Cadmium In The Water Body element.
Background technology
Cadmium In The Water Body is the very important problem that water body environment pollution faces in recent years.For the pollution level of Cadmium In The Water Body element being carried out to evaluation and the improvement of science, need to analyze the cadmium element content in water body and valence state, form etc.The method of measuring at present 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 harshness, reagent consumption are large, and what have need to adopt poisonous organic extractant and developer, produces secondary pollution.Majority method needs expensive large-scale instrument, method is all the pattern to lab analysis after employing on-site sampling in addition, can not realize scene, the real-time mode of measuring, sample transportation and processing procedure are easily introduced 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 example, for ocean maternal environment complicated and changeable: element morphology is affected greatly by space-time; Majority is again in interrelated, interactional state; In environment, temperature, pressure changes greatly, and accuracy and the reliability of its result are under suspicion, thereby can not definitely grasp seawater quality present situation and ANOMALOUS VARIATIONS thereof.
In recent years, along with the development of electronic technology, new material, new technology, new optical device, especially making rapid progress of computer technology, analyze the corresponding appearance of method of heavy metal in sea water element by automatic analyzer, although these technology have been broken away from some shortcomings of lab analysis, as long in the duration, analytic process is numerous and diverse, condition harshness etc., but the defect that it also exists, and poor stability, sensitivity and resolution are low, ion interference etc. is difficult to overcome, make it range of application and be restricted, could not be widely used.
Existing extracting process and device exist extraction efficiency low in addition, and layering is inhomogeneous, and organic solvent use amount is large, have the problem of secondary pollution.It is not high that the chromatography packed column using now has separating power, the defect that dead volume is large.
Summary of the invention
The invention provides a kind of liquid chromatogram mobile injected chemical luminescence method and measure the device and method of Cadmium In The Water Body, what it can solve that prior art exists can not work on the spot, analyzes the duration long, and analytic process is numerous and diverse, condition harshness, energy consumption are large, especially produce secondary pollution problems.Design extraction cell and chromatography packed column by novelty, solved existing extracting process and device and existed extraction efficiency low, layering is inhomogeneous, and organic solvent use amount is large, has the problem of secondary pollution; It is not high that the chromatography packed column that has solved present use has separating power, and disengaging time is long, and the defect that dead volume is large has realized efficient extraction, separated flow injected chemical luminescence method is measured Cadmium In The Water Body element fast.
In order to reach the object solving the problems of the technologies described above, technical scheme of the present invention is, liquid chromatogram mobile injected chemical luminescence method is measured 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, between chromatography packed column and sensing chamber and aforesaid liquid, connect by pipeline, 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 strata dividing plate, described upper strata dividing plate is to be made up of the material of 70%-80% methyl polysiloxane and 20%-30% polyglycol, described extraction lower floor is interval with multiple tracks lower floor dividing plate, described lower floor dividing plate is to be made up of the material of 20%-30% methyl polysiloxane and 70%-80% polyglycol, described air chamber is communicated with nitrogen, in the middle of described extraction lower floor and described air chamber, be provided with stainless steel microwell plate, be provided with entry to mixed solution in described extraction lower floor, be provided with organic phase outlet 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 are cylindrical, and extraction turbulent area is by reverse frustoconic and just truncated cone-shaped is opposed forms, and it is conical that described air chamber is.
Described filler is to be carrier by corrosive acid sodium, immobile liquid is to be made up of cyanopropyl 30%, phenyl methyl polysiloxane 50% and polyglycol 20%, described magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material of 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), continue to flow in pipeline with the mixed mixed solution of phosphoric acid, then mixes formation methacrylic acid diethylene glycol dilaurate complex compound with the methacrylic acid diethylene glycol dilaurate in complexing agent-methacrylic acid diethylene glycol dilaurate pipeline;
(4), mixed mixed solution continues to flow in pipeline, mix with the cyclohexane in cyclohexane pipeline again, together flow into extraction cell, below extraction cell, pass into nitrogen, bubbling 30-50s, static 30-50s again, solution layering, the organic phase that cyclohexane extraction methacrylic acid diethylene glycol dilaurate complex compound forms is on extraction upper strata;
(5), organic phase pump is transported to organic phase in the quantity tube of threeway sampling valve;
(6), quantity tube is filled with after sample, threeway sampling valve cuts out sample delivery passage, 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, sample interacts mutually with the fixing of packed column, distribute between mutually with fixing at mobile phase, because each component in sample is different from the affinity of fixing phase, therefore in sample each component by it different chromatography packed columns that successively flow out in two alternate affinity;
(7), from chromatography packed column flow out mix with current-carrying with the solution of separation component together with the sensing chamber of circulating, the photomultiplier in Electro-Optical Sensor Set detects the chemiluminescence signal of retention time 7-9min component in solution;
(8) light signal that the solution that, photomultiplier convection current is passed through sends gathers amplification, and convert electric signal to and send into microcomputer data processing equipment, data processing equipment calculates the blank signal obtaining 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 show, printout.
In technical scheme of the present invention, 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, made by the material that contains 75% methyl polysiloxane and 25% polyglycol, methyl polysiloxane lipophilicity, polyglycol water wettability, be conducive to like this organic phase and separate floating, extraction lower floor is provided with four layers of dividing plate, made by the material that contains 25% methyl polysiloxane and 75% polyglycol, being conducive to like this water sample separation floats downward, in the middle of extraction cell, extraction turbulent area is by two opposed formation of round platform, form from bottom to up the structure of first shrinking further expansion, 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.In the middle of the extraction lower floor of extraction cell and air chamber, be provided with stainless steel microwell plate, 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, it is carrier that filler uses corrosive acid sodium, immobile liquid is 30% cyanopropyl-50% phenyl methyl polysiloxane-20% polyglycol composition, magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material of 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 the thermodynamics and kinetics characteristic that affects post effect between the fixing phase of liquid phase packed column and mobile phase has effectively been improved in micro-magnetic field.Strengthened mobile phase and fixed the allocative efficiency between phase, having improved post effect, having ensured because each component in sample is different from the affinity of fixing phase, in sample, by it, the different priorities in two alternate affinity flow out chromatography packed columns to each component.
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 the calculating to described data processing equipment control, signal processing 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 forms in complex compound process with methacrylic acid diethylene glycol dilaurate under acid system, easily produce some organic by-products, this accessory substance likely strengthens or suppresses the chemiluminescence phenomenon of methacrylic acid diethylene glycol dilaurate complex compound and ethyl acetoacetate generation, system is brought to interference, the interference bringing in order to eliminate accessory substance, adopt liquid chromatogram mobile injection system, special liquid phase packed column has selectivity, different structure organism is carried out to selectivity exchange, according to different from exchanger affinity separately, there is the characteristic that retention time is different, packed column adopts the filler that contains magnetic Nano material in addition, coordinate and be with magnetic packed column, magnetic Nano material is under whole paramagnetic field action, produce micro-magnetic field, the thermodynamics and kinetics characteristic that affects post effect between the fixing phase of liquid phase packed column and mobile phase has effectively been improved in micro-magnetic field, mobile phase and the allocative efficiency of fixing between phase are strengthened, improve post effect, ensure because each component in sample is different from the affinity of fixing phase, in sample, by it, the different priorities in two alternate affinity flow out chromatography packed columns to each component.Liquid chromatography has highly sensitive, and analysis speed is fast, separates, so be all widely used in many scientific domains such as environmental chemistry, Food Chemistry, chemical industry, electronics, biological medicine, new material researchs when can realizing gas chromatography.Utilize liquid chromatogram mobile injection technique to separate fast in complex reaction process and form multiple organism, detect the method for the liquid chromatogram mobile injected chemical luminescence method mensuration Cadmium In The Water Body element of the chemiluminescence degree foundation of object generation by retention time.Adopt the present invention to measure Cadmium In The Water Body element and there is scene, quick, easy, sensitive feature.
Liquid chromatogram mobile injected chemical luminescence method is measured the method for Cadmium In The Water Body element by the luminous Photodetection system of integrated liquid chromatogram mobile injected chemical light, mechanical, electrical, computing machine forms.Can be divided into five parts by operational module:
Part I: extractive reaction system, comprise: water sample pump, phosphoric acid solution pump, methacrylic acid ethylene glycol bis ester solution pump, cyclohexane pump, extraction cell, under the acid system that in water sample, cadmium element provides at phosphoric acid, form complex compound with methacrylic acid diethylene glycol dilaurate, then in extraction cell, utilize cyclohexane extraction to form methacrylic acid diethylene glycol dilaurate formation 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, sample interacts mutually with the fixing of packed column, distribute between mutually with fixing at mobile phase, because each component in sample is different from the affinity of fixing phase, therefore in sample each component by it different chromatography packed columns that successively flow out in two alternate affinity;
Part III is flow injection part, be mainly ethyl acetoacetate under pumping action as one moving, without the continuous current-carrying of airspace, this current-carrying mixes by carrier band to sensing chamber successively with the sample of separating from liquid chromatography packed column.
Part IV: opto-electronic conversion and amplifier section, mainly adopt low-light photomultiplier as detecting element, carrier fluid circulation sensing chamber, the light signal of generation is transformed into electric signal immediately, and by continuous recording.
Part V is data acquisition, recording section, and this part completes collection, A/D conversion, transmission and the storage of electric signal.
Part VI is microcomputer data handling system, main being responsible for calculated the blank signal obtaining and sample signal, 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 again, and show, printout.
Because chemiluminescence reaction speed is very fast conventionally; so must ensure sample and mixing that luminescence reagent can fast, effectively, highly reappear; liquid chromatography separated flow injection technique has met 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 processes the method for measuring to Cadmium In The Water Body element by integrated abstraction technique, liquid chromatography isolation technics, Flow Injection Technique, chemiluminescence, electrooptical device, data acquisition, software.Method has scene, quick, 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 harshness, energy consumption are large, especially produce secondary pollution problems, are 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 developed and popularization in fields such as environmental analyses.
Brief description of the drawings
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, photodetection 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 outlet; 5-3, upper strata dividing plate; 5-4, extraction turbulent area; 5-5, lower floor's dividing plate; 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 outlet.
Embodiment
Referring to 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, extracting upper strata and extracting lower floor is cylindrical shape, and extraction turbulent area 5-4 is by reverse frustoconic and just truncated cone-shaped is opposed forms, and it is conical that described air chamber 5-7 is.Described extraction upper strata is interval with 4 unexposed layer dividing plate 5-3, described upper strata dividing plate 5-3 is made up of the material of 75% methyl polysiloxane and 25% polyglycol, described extraction lower floor is interval with the 4 dividing plate 5-5 of road lower floor, the described dividing plate 5-5 of lower floor is made up of the material of 25% methyl polysiloxane and 75% polyglycol, described air chamber 5-7 is communicated with nitrogen cylinder 6, referring to Fig. 2, in the middle of described extraction lower floor and described air chamber 5-7, be provided with stainless steel microwell plate 5-6, extraction lower floor on stainless steel microwell plate 5-6 is provided with entry to mixed solution 5-9, on extraction upper strata body under the dividing plate 5-3 of first upper strata, be provided with organic phase outlet 5-2.
Referring to 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 to be carrier by corrosive acid sodium, immobile liquid is to be made up of cyanopropyl 30%, phenyl methyl polysiloxane 50% and polyglycol 20%, described magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material of 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 the thermodynamics and kinetics characteristic that affects post effect between the fixing phase of liquid phase packed column and mobile phase has effectively been improved in micro-magnetic field.Strengthened mobile phase and fixed the allocative efficiency between phase, having improved post effect, having ensured because each component in sample is different from the affinity of fixing phase, in sample, by it, the different priorities in two alternate affinity flow out chromatography packed columns 7 to each component.
Referring to Fig. 1 and Fig. 2, a kind of liquid chromatogram mobile injected chemical luminescence method is measured 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, connect by pipeline between extraction cell 5, threeway sampling valve 3, chromatography packed column 7 and sensing chamber 19 and aforesaid liquid.
The method that adopts apparatus of the present invention to measure Cadmium In The Water Body element comprises following step:
(1), luminous agent-ethyl acetoacetate 18 under pump 17 effect 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), continue to flow in pipeline with the mixed mixed solution of phosphoric acid, 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 forms 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, quantity tube volume is 10 μ L;
(6), the quantity tube of threeway sampling valve 3 is filled with after sample, threeway sampling valve 3 cuts out sample delivery passage, 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, sample interacts mutually with the fixing of chromatography packed column 7, distribute between mutually with fixing at mobile phase, because each component in sample is different from the affinity of fixing phase, therefore in sample each component by it different chromatography packed columns 7 that successively flow out in two alternate affinity;
(7), from chromatography packed column 7 flow out mix with current-carrying with the solution of separation component together with the sensing chamber 19 of circulating, the photomultiplier in Electro-Optical Sensor Set 23 detects the chemiluminescence signal of retention time 8min component in solution;
(8) light signal that the solution that, photomultiplier convection current is passed through sends gathers amplification, and convert electric signal to and send into microcomputer data processing equipment, data processing equipment calculates the blank signal obtaining 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 show, 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 is selected 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 the calculating to described data processing equipment control, signal processing and Cadmium In The Water Body concentration by software programming.
The above, be only preferred embodiment of the present invention, is not the restriction of the present invention being made to other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.All technical solution of the present invention contents that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done 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 is measured 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, between chromatography packed column and sensing chamber and aforesaid liquid, connect by pipeline, 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 strata dividing plate, described upper strata dividing plate is to be made up of the material of 70%-80% methyl polysiloxane and 20%-30% polyglycol, described extraction lower floor is interval with multiple tracks lower floor dividing plate, described lower floor dividing plate is to be made up of the material of 20%-30% methyl polysiloxane and 70%-80% polyglycol, described air chamber is communicated with nitrogen, in the middle of described extraction lower floor and described air chamber, be provided with stainless steel microwell plate, be provided with entry to mixed solution in described extraction lower floor, be provided with organic phase outlet 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 is measured the device of Cadmium In The Water Body, it is characterized in that, described extraction upper strata and extraction lower floor are cylindrical, and extraction turbulent area is by reverse frustoconic and just truncated cone-shaped is opposed forms, and it is conical that described air chamber is.
3. a kind of liquid chromatogram mobile injected chemical luminescence method according to claim 2 is measured the device of Cadmium In The Water Body, it is characterized in that, described filler is to be carrier by corrosive acid sodium, immobile liquid is to be made up of cyanopropyl 30%, phenyl methyl polysiloxane 50% and polyglycol 20%, described magnetic Nano material uses dimethyl siloxane load to modify the ferroferric oxide magnetic nano-material of 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), continue to flow in pipeline with the mixed mixed solution of phosphoric acid, then mixes formation methacrylic acid diethylene glycol dilaurate complex compound with the methacrylic acid diethylene glycol dilaurate in complexing agent-methacrylic acid diethylene glycol dilaurate pipeline;
(4), mixed mixed solution continues to flow in pipeline, mix with the cyclohexane in cyclohexane pipeline again, together flow into extraction cell, below extraction cell, pass into nitrogen, bubbling 30-50s, static 30-50s again, solution layering, the organic phase that cyclohexane extraction methacrylic acid diethylene glycol dilaurate complex compound forms is on extraction upper strata;
(5), organic phase pump is transported to organic phase in the quantity tube of threeway sampling valve;
(6), quantity tube is filled with after sample, threeway sampling valve cuts out sample delivery passage, 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, sample interacts mutually with the fixing of chromatography packed column, distribute between mutually with fixing at mobile phase, because each component in sample is different from the affinity of fixing phase, therefore in sample each component by it different chromatography packed columns that successively flow out in two alternate affinity;
(7), from chromatography packed column flow out mix with current-carrying with the solution of separation component together with the sensing chamber of circulating, the photomultiplier in Electro-Optical Sensor Set detects the chemiluminescence signal of retention time 7-9min component in solution;
(8) light signal that the solution that, photomultiplier convection current is passed through sends gathers amplification, and convert electric signal to and send into microcomputer data processing equipment, data processing equipment calculates the blank signal obtaining 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 show, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410082138.0A CN103837632B (en) | 2014-03-07 | 2014-03-07 | Device and method for measuring cadmium in water through liquid chromatogram flow injection chemiluminescence |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410082138.0A CN103837632B (en) | 2014-03-07 | 2014-03-07 | Device and method for measuring cadmium in water through liquid chromatogram flow injection chemiluminescence |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103837632A true CN103837632A (en) | 2014-06-04 |
| CN103837632B CN103837632B (en) | 2015-06-24 |
Family
ID=50801346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410082138.0A Active CN103837632B (en) | 2014-03-07 | 2014-03-07 | Device and method for measuring cadmium in water through liquid chromatogram flow injection chemiluminescence |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103837632B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115151815A (en) * | 2020-02-25 | 2022-10-04 | 美迪恩斯生命科技株式会社 | Method for analyzing nucleic acid drug and the like |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017722A (en) * | 1991-04-04 | 2000-01-25 | Board Of Regents, The University Of Texas System | Luminous bacteria and methods for the isolation, identification and quantitation of toxicants |
| WO2001036963A2 (en) * | 1999-11-18 | 2001-05-25 | Gsf-Forschungszentrum Fur Umwelt Und Gesundheit Gmbh | Method for detecting noxious substances using plant cell suspensions |
| CN101294940A (en) * | 2008-06-12 | 2008-10-29 | 山东省科学院海洋仪器仪表研究所 | Method for measuring heavy metal in sea water by ion color spectrum flow injection chemiluminescence restraint method |
| CN102010370A (en) * | 2010-09-26 | 2011-04-13 | 云南烟草科学研究院 | Analytical reagent for heavy metal measurement as well as preparation method and application thereof |
| CN102590411A (en) * | 2012-01-16 | 2012-07-18 | 中国水产科学研究院黄海水产研究所 | Method for detecting divalent cadmium ion in aquatic product by using HPLC-ICP-MS coupling technique |
| CN103499569A (en) * | 2013-10-14 | 2014-01-08 | 山东省科学院海洋仪器仪表研究所 | Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury by inhibiting |
| CN103499570A (en) * | 2013-10-14 | 2014-01-08 | 山东省科学院海洋仪器仪表研究所 | Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury |
| CN103616365A (en) * | 2013-12-11 | 2014-03-05 | 山东省科学院海洋仪器仪表研究所 | Detection device and method for measuring lead in water by flow injection fluorescence quenching method |
-
2014
- 2014-03-07 CN CN201410082138.0A patent/CN103837632B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017722A (en) * | 1991-04-04 | 2000-01-25 | Board Of Regents, The University Of Texas System | Luminous bacteria and methods for the isolation, identification and quantitation of toxicants |
| WO2001036963A2 (en) * | 1999-11-18 | 2001-05-25 | Gsf-Forschungszentrum Fur Umwelt Und Gesundheit Gmbh | Method for detecting noxious substances using plant cell suspensions |
| CN101294940A (en) * | 2008-06-12 | 2008-10-29 | 山东省科学院海洋仪器仪表研究所 | Method for measuring heavy metal in sea water by ion color spectrum flow injection chemiluminescence restraint method |
| CN102010370A (en) * | 2010-09-26 | 2011-04-13 | 云南烟草科学研究院 | Analytical reagent for heavy metal measurement as well as preparation method and application thereof |
| CN102590411A (en) * | 2012-01-16 | 2012-07-18 | 中国水产科学研究院黄海水产研究所 | Method for detecting divalent cadmium ion in aquatic product by using HPLC-ICP-MS coupling technique |
| CN103499569A (en) * | 2013-10-14 | 2014-01-08 | 山东省科学院海洋仪器仪表研究所 | Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury by inhibiting |
| CN103499570A (en) * | 2013-10-14 | 2014-01-08 | 山东省科学院海洋仪器仪表研究所 | Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury |
| CN103616365A (en) * | 2013-12-11 | 2014-03-05 | 山东省科学院海洋仪器仪表研究所 | Detection device and method for measuring lead in water by flow injection fluorescence quenching method |
Non-Patent Citations (4)
| Title |
|---|
| GUANGYU YANG ET AL: "Study on solid phase extraction and graphite furnace atomic absorption spectrometry for the determination of nickel, silver, cobalt, copper, cadmium and lead with MCI GEL CHP 20Y as sorbent", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 162, no. 1, 15 February 2009 (2009-02-15), XP025782697, DOI: doi:10.1016/j.jhazmat.2008.05.007 * |
| K. A. HIGH ET AL: "Thermospray-Microatomizer Interface for the Determination of Trace Cadmium and Cadmium-Metallothionelns In Biological Samples with Flow Injection- and High-Performance Liquid Chromatography-Atomic Absorption Spectrometry", 《ANAL. CHEM.》, vol. 64, no. 24, 31 December 1992 (1992-12-31), XP000332402, DOI: doi:10.1021/ac00048a020 * |
| 台希 等: "固相萃取富集高效液相色谱法测定环境水样中的重金属元素", 《干旱环境监测》, vol. 18, no. 2, 15 June 2004 (2004-06-15) * |
| 王亮 等: "在线固相萃取富集反相液相色谱法测定水中的铅、镉、汞、银", 《分析化学》, vol. 32, no. 4, 25 April 2004 (2004-04-25) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115151815A (en) * | 2020-02-25 | 2022-10-04 | 美迪恩斯生命科技株式会社 | Method for analyzing nucleic acid drug and the like |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103837632B (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106841466B (en) | A kind of liquid chromatogram pre-column derivatization detecting water glyphosate | |
| CN106841334A (en) | It is a kind of can real time on-line monitoring contents of many kinds of heavy metal ion detecting system and method | |
| CN102928389A (en) | Device for quickly detecting impregnation amount in real time and using method thereof | |
| CN104792852A (en) | Algal toxin molecular imprinting chemoreceptor sensor as well as preparation method and application thereof | |
| CN103499569B (en) | Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury by inhibiting | |
| CN106338557A (en) | Method for determination of 55 volatile organic pollutants in soil | |
| CN101294940B (en) | Method for measuring heavy metal in sea water by ion color spectrum flow injection chemiluminescence restraint method | |
| CN103837632B (en) | Device and method for measuring cadmium in water through liquid chromatogram flow injection chemiluminescence | |
| CN107167545A (en) | A kind of method of total content of organic carbon in measure water | |
| CN102809558B (en) | Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way | |
| CN202710577U (en) | Peroxide online detection device | |
| CN202024965U (en) | Real-time on-line detecting device for concentration of nitrate ions in seawater | |
| CN102788782B (en) | Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode | |
| CN209589632U (en) | A kind of online headspace sampling device can be used for enhancing sensitivity for analysis | |
| CN103616365B (en) | Flow injection Fluorimetric Quenching Method measures pick-up unit plumbous in water and method | |
| CN100454005C (en) | Method for examining deposit or organic matter content in soil by ozone oxidation | |
| CN103499570B (en) | Portable injection chemiluminescence measures pick-up unit and the method for water body inorganic mercury | |
| CN2883386Y (en) | Microbe breathing rate analyzer based on bulbbler counting | |
| CN104977282B (en) | The device and method of selenium in molecular engram selection laser inductive fluorescence method measurement water body | |
| CN104569214A (en) | Method for measuring low-concentration p-xylene in metal ion and organism composite wastewater | |
| Kalyan et al. | Membrane optode for uranium (VI) ions preconcentration and quantification based on a synergistic combination of 4-(2-thiazolylazo)-resorcinol with 8-hydroxyquinaldine | |
| CN104267198A (en) | Automatic calibration device and method for volatile organic compound analyzer | |
| CN204203105U (en) | Water body ammonia-nitrogen content speed check reagent box | |
| CN106323932A (en) | Method for rapidly detecting arsanilic acid and roxarsone in water sample | |
| CN102798629B (en) | Method for measuring water sulfide concentration through flow injection chemiluminescence |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |