CN109765307B - Method for measuring hexachlorocyclohexane in water body - Google Patents
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Abstract
The invention discloses a method for measuring hexachlorocyclohexane in a water body, which is based on the fact that hexachlorocyclohexane and diethylenetriamine pentacarboxylate in the water body form a complex compound, firstly, the complex compound formed in the water body is rapidly enriched by an enrichment-elution mode, then, the enriched complex compound is eluted by the enrichment-elution mode, the eluted complex compound and polyhydroxyacrylic acid form a ternary complex compound, the complex compound and gloss fine oxidation generate chemiluminescence, meanwhile, the chemiluminescence intensity has a linear relation with the concentration of hexachlorocyclohexane in the water body, and a method for measuring hexachlorocyclohexane in the water body is established by utilizing a complexing-enrichment-elution-complexing-chemiluminescence technology. The method for measuring hexachlorocyclohexane in water has the characteristics of rapidness, simplicity, convenience, high accuracy and no secondary pollution.
Description
Technical Field
The invention relates to the field of environmental chemistry detection, in particular to a method for measuring hexachlorocyclohexane in a water body.
Background
The organochlorine pesticide hexachlorocyclohexane (666) is one of important contents in water environment monitoring. At present, the common method for measuring 666 in the water body is to carry back to a laboratory sampling gas chromatography after sampling, 666 in a water sample is extracted by normal hexane, purified and concentrated, and the content of each isomer is measured by using a packed column gas chromatography, wherein the total amount is the sum of the content of each isomer. The method is characterized by long duration, complicated analysis process, harsh conditions and large reagent consumption, and organic solvents harmful to human bodies are introduced in the pretreatment process of the method to different degrees, so that a large amount of reagents are wasted, and secondary pollution is generated. Meanwhile, the method needs expensive large-scale instruments, in addition, the method adopts a mode from field sampling to laboratory analysis, namely, a mode of field and real-time measurement cannot be realized, and other interference substances are easily introduced in the sample transportation process and the sample treatment process, so that the analysis accuracy is influenced. Therefore, the trace element analysis in the process cannot ensure that the possibility of secondary pollution cannot occur, so that the water quality status and the abnormal change thereof cannot be grasped exactly.
In recent years, with the development of electronic technology, new materials, new processes and new optical devices, particularly the change of computer technology, a method for analyzing the water 666 by an automatic analyzer has appeared correspondingly, although the technologies get rid of some defects of laboratory analysis, such as long duration, complicated analysis process, harsh conditions and the like, the technologies also have the defects of poor stability, low sensitivity, low resolution and the like which are difficult to overcome, so that the application range of the technologies is limited and the technologies cannot be widely applied.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for measuring hexachlorocyclohexane in a water body, so as to achieve the purposes of on-site measurement, rapidness, simplicity, convenience, sensitivity and no secondary pollution.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for measuring hexachlorocyclohexane in a water body comprises the following steps:
(1) mixing a water sample with a sodium carbonate-sodium bicarbonate solution serving as a buffer solution, and then mixing the mixture with a diethylenetriamine pentacarboxylate solution serving as a complexing agent in a pipeline, wherein the diethylenetriamine pentacarboxylate forms a complex with hexachlorocyclohexane in the water sample;
(2) the water sample forming the complex enters an enrichment-elution column, and catalysts Ni and SiO are added in the enrichment-elution column2Under the catalytic action of the mixture, the diethylenetriamine pentamethylene phosphonate composite material filled in the enrichment-elution column enters a complexPerforming high-efficiency selective enrichment;
(3) after the enrichment is finished, discharging a water sample, conveying the oxalic ester peroxide eluent through a pump to flow through an enrichment-elution column, and eluting the enriched complex into the eluent;
(4) continuously flowing the eluent in the pipeline, mixing the eluent with a buffer solution acetic acid-ammonium acetate solution and a complexing agent polyhydroxyacrylic acid solution in sequence, and forming a ternary complex under the pH condition provided by the buffer solution;
(5) the solution forming the ternary complex and the brightener lucigenin solution are mixed and then enter a detection chamber, the ternary complex and the lucigenin are oxidized to generate chemiluminescence, a photomultiplier collects and amplifies optical signals emitted by the solution passing through the current, converts the optical signals into electric signals and sends the electric signals to a data processing device, the data processing device calculates obtained blank signals and sample signals, and then the concentration of hexachlorocyclohexane in the water body is calculated according to the corresponding relation between the signal degree difference data and the signal degree difference data of the standard sample.
In the scheme, the flow rate of the water sample is 5.0-10 ml/min; the flow rate of the sodium carbonate-sodium bicarbonate solution is 0.1-0.5ml/min, and the concentration is (1.0-1.5) multiplied by 10－2mol/L and pH range of 8-9.
In the scheme, the flow of the complexing agent diethylenetriamine pentacarboxylate solution is 1.0-5.0ml/min, and the concentration is (0.5-1.0) multiplied by 10－2mol/L。
In the scheme, the flow rate of the eluent peroxyoxalate is 0.5-1.0ml/min, and the concentration is 2-5 mol/L.
In the scheme, the flow rate of the buffer solution acetic acid-ammonium acetate solution is 1.0-5.0ml/min, and the concentration is (10-20) multiplied by 10－2mol/L and pH range of 5-6.
In the scheme, the flow rate of the complexing agent polyhydroxyacrylic acid solution is 0.5-1.0ml/min, and the concentration is 0.1-0.3 mol/L.
In the scheme, the luminescent agent lucigenin is used as a carrier flow under the action of a pump, the flow rate is 0.1-0.3ml/min, and the concentration is 0.01-0.03 mol/L.
In the above scheme, the concentration-elution column contains diethylenetriamine pentamethylenePhosphonate composite material and catalysts Ni and SiO2The mass ratio of the mixture is 3:1, the material is granular, and the diameter is 400-600 microns.
In the scheme, during the enrichment process in the step (2), the temperature of the enrichment-elution column is 60-70 ℃, and the enrichment time is 5 min; during the elution process in the step (3), the temperature of the enrichment-elution column is 20-30 ℃.
In the above scheme, the pump is a peristaltic pump, and the pipeline is made of polytetrafluoroethylene material.
According to the technical scheme, the method for measuring hexachlorocyclohexane in the water body provided by the invention is a method for measuring hexachlorocyclohexane in the water body through a complexing-enriching-eluting-complexing technology, a flow injection technology, a photoelectric conversion device, data acquisition and software processing. The method has the advantages that the efficient enrichment and quick elution of trace hexachlorocyclohexane in water can be realized through the integrated design of complexation-enrichment-elution-complexation, the characteristics of automatic injection, controlled dispersion and accuracy and quickness are realized by combining the flow injection technology, and then a chemiluminescence method with high sensitivity and strong selectivity is adopted, so that the whole process has the characteristics of on-site, quickness, simplicity and sensitivity, the problems of incapability of on-site work, long analysis duration, complex analysis process, harsh conditions, high energy consumption, secondary pollution and the like in the prior art can be solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic flow chart of a method for measuring hexachlorocyclohexane in a water body, which is disclosed by the embodiment of the invention;
FIG. 2 is a schematic connection diagram of a device used in the method for measuring hexachlorocyclohexane in a water body disclosed by the embodiment of the invention.
In the figure, 1, water sample; 2. blank solution-distilled water; 3. a water sample pump; 4. buffer solution sodium carbonate-sodium bicarbonate; 5. a buffer pump I; 6. complexing agent diethylenetriamine pentacarboxylate solution; 7. a complexing agent pump I; 8. eluent 9 and an eluent pump; 10. a three-way sample injection valve; 11. an enrichment-elution column; 12. buffer solution acetic acid-ammonium acetate; 13. a buffer liquid pump II; 14. a complexing agent of a polyhydroxyacrylic acid solution; 15. a complexing agent pump II; 16. a luminescent agent; 17. a luminescent agent pump; 18. a waste liquid collector; 19. a photodetection device; 20. a detection chamber; 21. a photoelectric control device; 22. a data processing device; 23. a concentrated solution collector; 24. a temperature control device.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a method for measuring hexachlorocyclohexane in a water body, which has the characteristics of rapidness, simplicity, convenience and high accuracy as shown in figure 1.
As shown in FIG. 2, the method adopts the devices shown in FIG. 2 for connection, and specifically comprises an enrichment-elution column 11, a detection chamber 20, a photoelectric detection device 19, a temperature control device 24, a photoelectric control device 21, a data processing device 22, a water sample pump 3, a buffer pump 5, a complexing agent pump 7, an eluent pump 9, a buffer pump 13, a complexing agent pump 15, a luminescent agent pump 17, an enrichment liquid collector 23 and a waste liquid collector 18. The data processing device 22 realizes the control, signal processing and 666 concentration calculation of the device through software programming.
In this embodiment, the photomultiplier tube of the photodetector 19 is made of a hamamatsu Photosensor Modules H5784 Series.
The enrichment-elution column is connected with a water sample pipeline, a buffer solution pipeline I, a complexing agent pipeline I and an eluent pipeline through pipelines, the detection chamber is connected with a luminous agent pipeline, a complexing agent pipeline II, an eluent pipeline II and a buffer solution pipeline II through pipelines, and the enrichment-elution column is filled with diethylenetriamine pentamethylenephosphonate composite material and catalysts Ni and SiO2Mixture of the catalyst with SiO2Ni is added as a carrier, and the mass fraction of the Ni accounts for 10-15% of the total mass. DivinylTriamine penta methylene phosphonate composite material and catalyst Ni, SiO2The mass ratio of the mixture is 3:1, the material is granular, and the diameter is 400-600 microns, so that the water sample can freely flow through the gaps among the granules, and meanwhile, the large contact area between the water sample and the water sample is ensured. The enrichment-elution column is provided with a temperature control device, the upper part of the enrichment-elution column is provided with a water sample inlet and an eluent inlet, the two inlets can share one inlet, the switching of the entering solution is carried out through a three-way sample injection valve, the lower part of the enrichment-elution cavity column is provided with an eluent outlet and a water sample outlet, and the two outlets can share one outlet. The pump is a peristaltic pump, and the pipeline is made of polytetrafluoroethylene material
As shown in FIG. 1, the specific process of the method for measuring hexachlorocyclohexane in water body is as follows:
(1) the water sample 1 is mixed with a sodium carbonate-sodium bicarbonate solution 4 in a buffer solution pipeline I under the action of a water sample pump 3, the flow rate of the water sample is controlled to be 5.0-10ml/min, the flow rate of the sodium carbonate-sodium bicarbonate solution is controlled to be 0.1-0.5ml/min by the buffer pump I5, and the concentration is (1.0-1.5) multiplied by 10－2mol/L, and the pH range is 8-9; continuously flowing in the pipeline after mixing, mixing with a complexing agent diethylenetriamine pentacarboxylate solution 6, controlling the flow of the complexing agent diethylenetriamine pentacarboxylate solution to be 1.0-5.0ml/min by a complexing agent pump I7, and controlling the concentration to be (0.5-1.0) multiplied by 10－2mol/L. Under the pH value provided by a sodium carbonate-sodium bicarbonate solution, diethylenetriamine pentacarboxylate and hexachlorocyclohexane in a water sample form a complex;
(2) the water sample forming the complex enters an enrichment-elution column 11 through a three-way sample injection valve 10, and catalysts Ni and SiO are contained in the enrichment-elution column 112Under the catalytic action of the mixture, the diethylenetriamine pentamethylene phosphonate composite material filled in the enrichment-elution column carries out high-efficiency selective enrichment on the complex; the temperature control device 24 controls the temperature of the enrichment-elution column to be 60-70 ℃, and the enrichment time is 5min, so that the composite material and a complex in a water sample can be stably bonded under the action of a catalyst to complete adsorption;
(3) after enrichment is finished, discharging a water sample into an enrichment liquid collector 23, switching a three-way sample injection valve 10, allowing an eluent of oxalic ester peroxide 8 to flow through an enrichment-elution column 11 under the conveying of an eluent pump 9, wherein the flow rate of the eluent of oxalic ester peroxide is 0.5-1.0ml/min, the concentration of the eluent of the oxalic ester peroxide is 2-5mol/L, and eluting an enriched complex into an eluent; during the elution process, the temperature control device 24 controls the temperature of the enrichment-elution column to be 20-30 ℃, so that the action force of the eluent to adsorb the complex in the water sample is ensured to be greater than the adsorption force of the eluent and the composite material under the action of the catalyst, and the high-efficiency elution can be realized.
(4) The eluent continuously flows in the pipeline, is mixed with a buffer solution acetic acid-ammonium acetate solution 12 and a complexing agent polyhydroxyacrylic acid solution 14 in sequence, and forms a ternary complex under the pH condition provided by the buffer solution; the second buffer pump 13 controls the flow rate of the acetic acid-ammonium acetate solution of the buffer solution to be 1.0-5.0ml/min, and the concentration to be (10-20) multiplied by 10－2mol/L, and the pH range is 5-6; the second complexing agent pump 15 controls the flow of the polyhydroxy acrylic acid solution of the complexing agent to be 0.5-1.0ml/min and the concentration to be 0.1-0.3 mol/L.
(5) The solution forming the ternary complex and the luminescent agent lucigenin solution 16 are mixed and then enter the detection chamber 20, the luminescent agent lucigenin is used as a carrier under the action of a luminescent agent pump 17, the flow rate is 0.1-0.3ml/min, and the concentration is 0.01-0.03 mol/L. The ternary complex and the gloss essence are oxidized to generate chemiluminescence, weak light signals are gathered by an optical lens and guided into a photomultiplier, under the control of a photoelectric control device 21, the light signals are processed and converted into electric signals by the photomultiplier in a photoelectric detection device 19 to be output, the output electric signals are converted by a weak signal amplification circuit, the electric signals are amplified to a certain voltage amplitude and sent to an A/D conversion channel of a data processing device 22 to be subjected to quantization and integration processing, and the processed waste liquid enters a waste liquid collector 18. And measuring the measured result of the blank solution distilled water 2 after the above process by the same method, calculating the obtained blank signal and the sample signal by the data processing device, calculating the concentration of hexachlorocyclohexane in the water body according to the corresponding relation of the signal degree difference data and the signal degree difference data of the standard sample, and printing and outputting.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for measuring hexachlorocyclohexane in a water body is characterized by comprising the following steps:
(1) mixing a water sample with a sodium carbonate-sodium bicarbonate solution serving as a buffer solution, and then mixing the mixture with a diethylenetriamine pentacarboxylate solution serving as a complexing agent in a pipeline, wherein the diethylenetriamine pentacarboxylate forms a complex with hexachlorocyclohexane in the water sample;
(2) the water sample forming the complex enters an enrichment-elution column, and catalysts Ni and SiO are added in the enrichment-elution column2Under the catalytic action of the mixture, the diethylenetriamine pentamethylene phosphonate composite material filled in the enrichment-elution column carries out high-efficiency selective enrichment on the complex;
(3) after the enrichment is finished, discharging a water sample, conveying the oxalic ester peroxide eluent through a pump to flow through an enrichment-elution column, and eluting the enriched complex into the eluent;
(4) continuously flowing the eluent in the pipeline, mixing the eluent with a buffer solution acetic acid-ammonium acetate solution and a complexing agent polyhydroxyacrylic acid solution in sequence, and forming a ternary complex under the pH condition provided by the buffer solution;
(5) the solution forming the ternary complex and the brightener lucigenin solution are mixed and then enter a detection chamber, the ternary complex and the lucigenin are oxidized to generate chemiluminescence, a photomultiplier collects and amplifies optical signals emitted by the solution passing through the current, converts the optical signals into electric signals and sends the electric signals to a data processing device, the data processing device calculates obtained blank signals and sample signals, and then the concentration of hexachlorocyclohexane in the water body is calculated according to the corresponding relation between the signal degree difference data and the signal degree difference data of the standard sample.
2. The method for measuring hexachlorocyclohexane in a water body according to claim 1, wherein the flow rate of the water sample is 5.0-10 ml/min; the flow rate of the sodium carbonate-sodium bicarbonate solution is 0.1-0.5ml/min, and the concentration is 1.0 multiplied by 10－2-1.5×10－2mol/L and pH range of 8-9.
3. The method of claim 1, wherein the complexing agent diethylenetriamine pentacarboxylate solution has a flow rate of 1.0-5.0ml/min and a concentration of 0.5 x 10－2-1.0×10－2mol/L。
4. The method as claimed in claim 1, wherein the flow rate of the eluent peroxyoxalate is 0.5-1.0ml/min, and the concentration is 2-5 mol/L.
5. The method for measuring hexachlorocyclohexane in water body according to claim 1, wherein the flow rate of the buffer solution acetic acid-ammonium acetate solution is 1.0-5.0ml/min, and the concentration is 10 x 10－2-20×10－2mol/L and pH range of 5-6.
6. The method for measuring hexachlorocyclohexane in a water body according to claim 1, wherein the flow rate of the complexing agent polyhydroxyacrylic acid solution is 0.5-1.0ml/min, and the concentration is 0.1-0.3 mol/L.
7. The method for measuring hexachlorocyclohexane in a water body according to claim 1, wherein the luminescent agent lucigenin is used as a carrier flow under the action of a pump, the flow rate is 0.1-0.3ml/min, and the concentration is 0.01-0.03 mol/L.
8. The method for measuring hexachlorocyclohexane in water according to claim 1, wherein said enrichment-elution column contains DTPMPA composite material and catalysts Ni and SiO2The mass ratio of the mixture is3:1, the material is granular and has the diameter of 400-600 microns.
9. The method for measuring hexachlorocyclohexane in a water body according to claim 1, wherein the temperature of the enrichment-elution column during the enrichment process in step (2) is 60-70 ℃ and the enrichment time is 5min, and the temperature of the enrichment-elution column during the elution process in step (3) is 20-30 ℃.
10. The method of claim 1, wherein the pump is a peristaltic pump and the conduit is made of polytetrafluoroethylene.
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| SU1727053A1 (en) * | 1990-03-26 | 1992-04-15 | Всесоюзный научный центр медицинской реабилитации и физической терапии | Method of organochlorine pesticides determination in the medicinal peloids |
| CN1164941C (en) * | 2001-08-23 | 2004-09-01 | 中国科学院南京土壤研究所 | Determination method of trace organic chlorine pesticide and polychlorobiphenyl residual amount |
| MY161534A (en) * | 2010-05-25 | 2017-04-28 | Genentech Inc | Methods of purifying polypeptides |
| CN102636603B (en) * | 2011-02-12 | 2014-05-07 | 湖北省烟草科研所 | Method for detecting organochlorine pesticide residue in soil |
| CN104316713B (en) * | 2014-10-14 | 2016-05-18 | 山东省科学院海洋仪器仪表研究所 | Device and the measuring method thereof of zinc in flow Injection Spectrophotometry for Determination water gaging body |
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