CN102809558B - Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way - Google Patents
Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way Download PDFInfo
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Abstract
The invention provides a method for measuring polycyclic aromatic hydrocarbon (PAHs) of sea water in a flow injection chemiluminescence way. The method adopts the scheme that the PAHs of the sea water is quickly enriched and eluted in an enrichment and elution way; and a chemiluminescence signal is detected via a chemiluminescence system formed by super oxidized oxalate, hydrogen peroxide and the PAHs, so that the method for measuring the PAHs of the sea water in the flow injection chemiluminescence way is achieved. The method for measuring the PAHs of the sea water has characteristics of site operation, speediness, simplicity and sensitivity.
Description
Technical field
The present invention relates to environmental chemistry monitoring technical field, specifically relate to measure the method for Polynuclear Aromatic Hydrocarbons In Seawater.
Background technology
Sea trace organic pollutant in water-palycyclic aromatic (Polycyclic Aromatic Hydrocarbons, PAHs) due to its persistence, the characteristic of bioconcentration and long Distance Transmission, has been put into screen priority pollutants list, is ocean water quality routine monitoring important parameter.Classic method mainly adopts the large-scale instrument and equipments such as chromatography of gases (GC), liquid chromatography mass combined instrument (HPLC-MS) and meteorological chromatograph-mass spectrometer (GC-MS), and sample need to separate detection after complicated pre-treatment in laboratory.Seawater sample matrix complexity, salinity are many, pretreatment process the more than 60% of whole analytic process that accounts for consuming time of sample, the equipment of process need complexity and efficiency are not high yet, exist simultaneously and use a large amount of poisonous organic solvents, complex operation step, easily make the shortcomings such as volatile components loss, directly have influence on precision of analysis and reliability.Instrument complexity used, expensive in addition, can not realize automatically, online, and the real time measure, is difficult in real time, reflects comprehensively, truly the dynamic change of organic contaminant-palycyclic aromatic in ocean, can not specify it to marine pollution degree.
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 organic contaminant-palycyclic aromatic 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, matrix interference etc. is difficult to overcome, make it range of application and be restricted, could not be widely used.
Summary of the invention
The invention provides a kind of portable injection chemiluminescence mode and measure the method for Polynuclear Aromatic Hydrocarbons In Seawater, 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.
In order to reach the object solving the problems of the technologies described above, technical scheme of the present invention is, a kind of portable injection chemiluminescence mode is measured the method for seawater palycyclic aromatic, described method adopts pick-up unit, described pick-up unit comprises eluent feeder, threeway sampling valve, enrichment wash-out post, sensing chamber, Electro-Optical Sensor Set, control device, microcomputer data handling system, carry the high pressure pump A of water sample, carry the high pressure pump B of eluent, carry peroxyoxalate solution pump and superoxol pump, described sensing chamber is by pipeline and enrichment wash-out post, peroxyoxalate solution pipeline, superoxol pipeline connects, described method is carried out in the steps below by described pick-up unit:
(1) threeway sampling valve is opened water sample transfer pipeline, high pressure pump A carries the enrichment wash-out post after water sample circulation threeway sampling valve, enrichment wash-out post inside is filled with the activated charcoal of polysiloxane crown ether composite coating, and there is temperature regulating device, carry out temperature control in enrichment and elution process, enrichment wash-out post carries out efficient selective enrichment to palycyclic aromatic in water body, and the enrichment wash-out post after water sample circulation threeway sampling valve carries out enrichment 150-200s;
(2) after enrichment completes, threeway sampling valve cuts out water sample transfer pipeline, opens eluent pipeline, eluent is the enrichment wash-out post that circulates under high pressure pump B carries, the palycyclic aromatic of eluent wash-out enrichment, enters in eluent, and described eluent is normal hexane;
(3) eluent that flows out enrichment wash-out post continues to flow at pipeline, mix with peroxyoxalate solution in peroxyoxalate solution pipeline and superoxol pipeline and superoxol respectively again, together flow into sensing chamber, the chemiluminescence signal that the reaction system that in the photomultiplier detection solution in Electro-Optical Sensor Set, peroxyoxalate and hydrogen peroxide and palycyclic aromatic form produces;
(4) 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 handling system, microcomputer data handling system is calculated the blank signal obtaining and sample signal, again according to the signal difference data corresponding relation of signal difference data and standard model, calculate the concentration of Polynuclear Aromatic Hydrocarbons In Seawater, and show, printout.
In the present invention, also have following technical characterictic, in enrichment process, water sample liquid inventory is 30-50ml/min.
In the present invention, also have following technical characterictic, described eluent is normal hexane, and flow is 1.0-5.0ml/min.
In the present invention, also have following technical characterictic, in enrichment process, the control temperature of enrichment wash-out post is at 60-70 DEG C, and in elution process, enrichment wash-out post temperature control is at 20-30 DEG C.
In the present invention, also have following technical characterictic, described peroxyoxalate liquid inventory is 0.5-1.0ml/min, and concentration is (2-3) × 10
-2mol/L.
In the present invention, also have following technical characterictic, described superoxol flow is 0.25-0.5ml/min, and concentration is (20-30) × 10
-3mol/L.
In the present invention, also have following technical characterictic, described enrichment wash-out column internal diameter scope is 9-11mm, and length is 95-105mm.
In the present invention, also have following technical characterictic, described high pressure pump A, B are mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline all adopts polytetrafluoroethylmaterial material to make.
In the present invention, also there is following technical characterictic, utilize microcomputer data handling system, realize the calculating to the control of described microcomputer data handling system, signal processing and palycyclic aromatic concentration by software programming.
In the present invention, also have following technical characterictic, photomultiplier adopts Japanese shore pine Photosensor Modules H5784Series.
Utilize the high sensitivity of chemiluminescence reaction to become the desirable means that present analysis is measured.Peroxyoxalate-hydrogen peroxide-fluorescent material luminescence system is the non-enzymatic catalysis chemiluminescence reaction that current luminescence efficiency is the highest, its quantum yield reaches 25%, palycyclic aromatic is a kind of typical fluorescent material, utilizing the luminescence system measurement palycyclic aromatic concentration that peroxyoxalate and hydrogen peroxide and palycyclic aromatic form is a kind of very effective means, has a good application prospect
Adopt in addition enrichment wash-out post, the inner activated charcoal of filling polysiloxane crown ether composite coating of enrichment wash-out post, polysiloxane crown ether composite coating has absorption property very efficiently to palycyclic aromatic, and also very good to its selectivity, by controlling enrichment wash-out column temperature within the scope of 60-70 DEG C, adsorption efficiency is higher; Adopting eluent is the palycyclic aromatic that normal hexane carries out wash-out absorption, and temperature control is within the scope of 20-30 DEG C, and elution efficiency is very high.
Utilize palycyclic aromatic in enrichment wash-out Flow Injection Technique fast enriching wash-out water body, what the luminescence system forming by peroxyoxalate and hydrogen peroxide and palycyclic aromatic detected that chemiluminescence signal sets up measures the method for Polynuclear Aromatic Hydrocarbons In Seawater from portable injection chemiluminescence mode.The present invention measures Polynuclear Aromatic Hydrocarbons In Seawater and has scene, quick, easy, sensitive feature.
Portable injection chemiluminescence mode is measured the method for Polynuclear Aromatic Hydrocarbons In Seawater by the integrated portable injection chemiluminescence Photodetection system light, mechanical, electrical, computing machine forms.Can be divided into five parts by operational module:
Part I is flow injection part, mainly peroxyoxalate and hydrogen peroxide system as one moving, without the continuous current-carrying of airspace, peroxyoxalate and hydrogen peroxide generation chemical reaction in current-carrying, finally mix with palycyclic aromatic, by carrier band in sensing chamber.
Part II: enrichment elution system, comprising: high pressure pump, eluent (normal hexane), threeway sampling valve, enrichment wash-out post elute the sample that comprises palycyclic aromatic and be injected in current-carrying from enrichment wash-out post.
Part III: 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 IV is data acquisition, recording section, and this part completes collection, A/D conversion, transmission and the storage of electric signal.
Part V is microcomputer data handling system, main being responsible for calculated the blank signal obtaining and sample signal, according to the signal difference data corresponding relation of signal difference data and standard model, calculate the concentration of Polynuclear Aromatic Hydrocarbons In Seawater 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; Flow Injection Technique has met this requirement; therefore combining with chemiluminescence analysis by enrichment wash-out post Flow Injection Technique, to measure the method for Polynuclear Aromatic Hydrocarbons In Seawater not only highly sensitive for the portable injection chemiluminescence mode 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 Polynuclear Aromatic Hydrocarbons In Seawater by integrated enrichment wash-out column technology, Flow Injection Technique, chemiluminescence, electrooptical device, data acquisition, software.By the integrated design of enrichment wash-out post, can realize Determination of Trace Polycyclic Aromatic Hydrocarbons efficiently concentrating in seawater and there is automatic injection with quick elution of bound Flow Injection Technique, controlled dispersion and accurately feature fast, adopt again sensitive chemical luminescence detection method, therefore utilize integrated enrichment wash-out column technology, the method that the portable injection chemiluminescence mode of setting up by detection chemiluminescence degree is again measured Polynuclear Aromatic Hydrocarbons In Seawater has scene, fast, easy, sensitive feature, what it can solve that prior art exists can not work on the spot, analyze the duration long, analytic process is numerous and diverse, condition harshness, energy consumption is large, especially produce secondary pollution problems, current very effective express-analysis means, it is 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. peroxyoxalate solution; 2. peroxyoxalate solution peristaltic pump; 3. superoxol; 4. superoxol peristaltic pump; 5. water sample solution; 6. high pressure pump A; 7. eluent feeder; 8. high pressure pump B; 9. threeway sampling valve; 10. enrichment-wash-out post; 11. liquid waste collectors; 12. sensing chamber; 13. Electro-Optical Sensor Sets; 14. control device; 15. microcomputer data handling systems.
Embodiment
Referring to Fig. 1 and Fig. 2, the inventive method comprises following step:
(1) threeway sampling valve 10 is opened water sample transfer passage, high pressure pump A6 carries the enrichment wash-out post 10 after water sample circulation threeway sampling valve 9, the inner activated charcoal of filling polysiloxane crown ether composite coating of enrichment wash-out post 10, and there is temperature regulating device, can be under suitable temperature conditions to water body in palycyclic aromatic carry out efficient selective enrichment, the enrichment wash-out post 10 of water sample circulation threeway sampling valve carries out enrichment 3min;
(2) after enrichment completes, threeway sampling valve 9 cuts out water sample transfer passage, opens eluent channel, normal hexane in eluent feeder 7 is under high pressure pump B8 carries, circulation enrichment wash-out post 10, the palycyclic aromatic of eluent wash-out enrichment, enters in eluent;
(3) eluent that flows out enrichment wash-out post 10 continues to flow at pipeline, in the peroxyoxalate solution pipeline of carrying with peroxyoxalate solution peristaltic pump 2 and superoxol peristaltic pump 4 respectively again and superoxol pipeline, peroxyoxalate solution 1 and superoxol 3 mix, together flow into sensing chamber 12, the chemiluminescence signal that the reaction system that in the photomultiplier detection solution in Electro-Optical Sensor Set 13, peroxyoxalate and hydrogen peroxide and palycyclic aromatic form produces;
(4) 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 handling system 15, microcomputer data handling system 15 is calculated the blank signal obtaining and sample signal, again according to the signal difference data corresponding relation of signal difference data and standard model, calculate the concentration of Polynuclear Aromatic Hydrocarbons In Seawater, and show, printout.
In the above-described embodiments:
In described enrichment process, water sample liquid inventory is 30ml/min.
In described elution process, eluent is normal hexane, and flow is 1.0ml/min.
Described enrichment wash-out post 10 has temperature regulating device, and in enrichment process, enrichment wash-out post 10 temperature controls are at 60 DEG C, and in elution process, enrichment wash-out post 10 temperature controls are at 20 DEG C.
Described peroxyoxalate liquid inventory is 0.5ml/min, and concentration is 2 × 10
-2mol/L.
Described superoxol flow is 0.25ml/min, and concentration is 20 × 10
-3mol/L.
Enrichment wash-out post 10 internal diameters after described threeway sampling valve 9 are 10mm, and length is 100mm.
Described high pressure pump A6 and high pressure pump B8 are mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline all adopts polytetrafluoroethylmaterial material to make.
Utilize microcomputer data handling system 15, realize the calculating of control to microcomputer data handling system 15, signal processing, palycyclic aromatic concentration by software programming.
Photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
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.But, 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 (8)
1. a portable injection chemiluminescence mode is measured the method for seawater palycyclic aromatic, it is characterized in that, described method adopts pick-up unit, described pick-up unit comprises eluent feeder, threeway sampling valve, enrichment wash-out post, sensing chamber, Electro-Optical Sensor Set, control device, microcomputer data handling system, carry the high pressure pump A of water sample, carry the high pressure pump B of eluent, carry peroxyoxalate solution pump and superoxol pump, described sensing chamber is by pipeline and enrichment wash-out post, peroxyoxalate solution pipeline, superoxol pipeline connects, described method is carried out in the steps below by described pick-up unit:
(1) threeway sampling valve is opened water sample transfer pipeline, high pressure pump A carries the enrichment wash-out post after water sample circulation threeway sampling valve, enrichment wash-out post inside is filled with the activated charcoal of polysiloxane crown ether composite coating, and there is temperature regulating device, carry out temperature control in enrichment and elution process, enrichment wash-out post carries out efficient selective enrichment to palycyclic aromatic in water body, and the enrichment wash-out post after water sample circulation threeway sampling valve carries out enrichment 150-200s;
(2) after enrichment completes, threeway sampling valve cuts out water sample transfer pipeline, opens eluent pipeline, the eluent enrichment wash-out post that circulates under high pressure pump B carries, and the palycyclic aromatic of eluent wash-out enrichment, enters in eluent, and described eluent is normal hexane;
(3) eluent that flows out enrichment wash-out post continues to flow at pipeline, mix with peroxyoxalate solution in peroxyoxalate solution pipeline and superoxol pipeline and superoxol respectively again, together flow into sensing chamber, the chemiluminescence signal that the reaction system that in the photomultiplier detection solution in Electro-Optical Sensor Set, peroxyoxalate and hydrogen peroxide and palycyclic aromatic form produces;
(4) 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 handling system, microcomputer data handling system is calculated the blank signal obtaining and sample signal, again according to the signal difference data corresponding relation of signal difference data and standard model, calculate the concentration of Polynuclear Aromatic Hydrocarbons In Seawater, and show, printout;
Described peroxyoxalate liquid inventory is 0.5-1.0ml/min, and concentration is (2-3) × 10
-2mol/L; Described superoxol flow is 0.25-0.5ml/min, and concentration is (20-30) × 10
-3mol/L.
2. method according to claim 1, is characterized in that, in enrichment process, water sample liquid inventory is 30-50ml/min.
3. method according to claim 1, is characterized in that, described eluent is normal hexane, and flow is 1.0-5.0ml/min.
4. method according to claim 1, is characterized in that, in enrichment process, the control temperature of enrichment wash-out post is at 60-70 DEG C, and in elution process, enrichment wash-out post temperature control is at 20-30 DEG C.
5. method according to claim 1, is characterized in that, described enrichment wash-out column internal diameter scope is 9-11mm, and length is 95-105mm.
6. method according to claim 1, is characterized in that, described high pressure pump A, B are mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline all adopts polytetrafluoroethylmaterial material to make.
7. method according to claim 1, is characterized in that, photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
8. according to the method described in any one claim in claim 1-7, it is characterized in that, utilize microcomputer data handling system, realize the calculating to the control of described microcomputer data handling system, signal processing and palycyclic aromatic concentration by software programming.
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| CN103837525B (en) * | 2014-03-07 | 2016-01-20 | 山东省科学院海洋仪器仪表研究所 | Enrichment elution flow injected chemical luminescence method measures the device and method of the total chromium of water body |
| CN104215726A (en) * | 2014-09-19 | 2014-12-17 | 山东省科学院海洋仪器仪表研究所 | Method for extracting and enriching polycyclic aromatic hydrocarbons in seawater |
| CN104865237A (en) * | 2015-05-25 | 2015-08-26 | 上海应用技术学院 | Device and method for detecting polycyclic aromatic hydrocarbon in water sample on site |
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| US5298427A (en) * | 1990-04-24 | 1994-03-29 | The Board Of Trustees Of The University Of Arkansas | Chemiluminescent detection of amino acids |
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