CN112268896A - Device and method for detecting concentration of trace hydrogen peroxide in surface water by adopting chemiluminescence reagent - Google Patents
Device and method for detecting concentration of trace hydrogen peroxide in surface water by adopting chemiluminescence reagent Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002352 surface water Substances 0.000 title claims abstract description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 78
- 230000002572 peristaltic effect Effects 0.000 claims description 33
- RXNXLAHQOVLMIE-UHFFFAOYSA-N phenyl 10-methylacridin-10-ium-9-carboxylate Chemical compound C12=CC=CC=C2[N+](C)=C2C=CC=CC2=C1C(=O)OC1=CC=CC=C1 RXNXLAHQOVLMIE-UHFFFAOYSA-N 0.000 claims description 29
- 238000001514 detection method Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000010354 integration Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000011002 quantification Methods 0.000 claims 2
- 239000000523 sample Substances 0.000 description 20
- 238000004891 communication Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- -1 azidine ester Chemical class 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- MXZACTZQSGYANA-UHFFFAOYSA-N chembl545463 Chemical compound Cl.C1=CC(OC)=CC=C1C(N=C1)=CN2C1=NC(C)=C2O MXZACTZQSGYANA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- NLOSEEJQYDRLLE-UHFFFAOYSA-N Cl.CC1=NC=2N(C=C(NC2)C2=CC=C(C=C2)C)C1=O Chemical compound Cl.CC1=NC=2N(C=C(NC2)C2=CC=C(C=C2)C)C1=O NLOSEEJQYDRLLE-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical class C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-O acridine;hydron Chemical compound C1=CC=CC2=CC3=CC=CC=C3[NH+]=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-O 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KNJDBYZZKAZQNG-UHFFFAOYSA-N lucigenin Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.C12=CC=CC=C2[N+](C)=C(C=CC=C2)C2=C1C1=C(C=CC=C2)C2=[N+](C)C2=CC=CC=C12 KNJDBYZZKAZQNG-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CYAJEMFRSQGFIG-ISWIILBPSA-N microcystin-LA Natural products CO[C@@H](Cc1ccccc1)[C@@H](C)C=C(C)C=C[C@H](NC(=O)CNC(=O)[C@@H](C)[C@@H](NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@@H](C)C(=O)O)C(=O)O)[C@H](C)C(=O)N CYAJEMFRSQGFIG-ISWIILBPSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002912 oxalic acid derivatives Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to a device and a method for detecting the concentration of trace hydrogen peroxide in surface water by adopting a chemiluminescent reagent. The device comprises a water body container bottle to be detected, a carrier solution container bottle, an electromagnetic switching valve, a quantitative ring, a mixing cavity, a spiral light-emitting tube, a chemical luminescent reagent container bottle, a sodium carbonate solution container bottle, a photon counter and a computer. The first flow path of the electromagnetic switching valve is connected with the outlet of the water container bottle to be tested, the second flow path and the seventh flow path are respectively connected with a waste liquid bottle, the third flow path is connected with the second interface of the quantitative ring, the fourth flow path is connected with the inlet of the mixing cavity, the sixth flow path is connected with the outlet of the spiral light-emitting tube, the ninth flow path is connected with the inlet of the carrier solution container bottle, and the tenth flow path is connected with the first interface of the quantitative ring. The outlet of the chemical luminous reagent container bottle is connected with the inlet of the mixing cavity, the outlet of the mixing cavity is connected with the inlet of the spiral luminous tube, and the outlet of the sodium carbonate solution container bottle is connected with the inlet of the spiral luminous tube. The invention can quantitatively detect the concentration of trace hydrogen peroxide in surface water.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a device and a method for detecting the concentration of trace hydrogen peroxide in surface water by adopting a chemiluminescent reagent.
Background
Under the direct irradiation of sunlight, organic matters (CDOM) in the water body can generate trace hydrogen peroxide (H) through a series of complex photoinduced electron transfer reactions (equation 1-3)2O2) Generally in a concentration range of about-10-10-10-6And M. In addition to this, H is formed by radical reactions in the atmospheric environment2O2And can also enter the surface water system through precipitation.
CDOM+hν→CDOM·-+CDOM·+ (1)
CDOM·-+O2→CDOM+O2 ·- (2)
2O2 ·-+2H+→H2O2+O2 (3)
H2O2As a stronger oxidant, it is miscible with water in any proportion. A number of studies have demonstrated that H2O2Can generate important influence on the environment by changing the distribution form and the biological toxicity of the metal, and simultaneously H2O2And can also contribute to the degradation behavior of man-made and natural organic matters. In the Fenton process of sewage treatment, H is also required to pass2O2To generate HO·Degrade pollutants, thereby accurately measuring H in the water body2O2The content has been a hot spot for industrial application and scientific research.
Conventional iodometry for H2O2Although widely used, the detection limit is higher (10)-6M) has the defect that the micro-H in surface water cannot be directly measured2O2And (4) concentration. And H2O2The sensors are expensive, and the devices are complex, so that the sensors are difficult to be applied to environmental monitoring of surface water. The chemiluminescence method becomes trace H in the environmental water body due to high sensitivity and simple operation2O2The detection is preferred, but the existing luminescent reagent luminol,Oxalic acid derivatives and lucigenin luminescent reagents are easily interfered by metal ions, and the defect that the chemiluminescence method is limited in H in surface water2O2And (5) popularization of detection.
Therefore, a more sensitive and reliable chemiluminescence reagent-based quantitative detection of trace H is realized2O2The concentration method and the concentration device have important application value for treatment technology and scientific research of natural water body.
Disclosure of Invention
The invention aims to provide a device and a method for detecting the concentration of trace hydrogen peroxide in surface water by using a chemiluminescent reagent, and the device and the method can be used for quantitatively detecting the concentration of trace hydrogen peroxide in surface water.
In order to achieve the purpose, the invention adopts the following technical scheme:
the device for detecting the concentration of trace hydrogen peroxide in surface water by adopting a chemiluminescent reagent comprises a water body container bottle to be detected, a carrier solution container bottle, an electromagnetic switching valve, a quantitative ring, a mixing cavity, a spiral light-emitting tube, a chemiluminescent reagent container bottle, a sodium carbonate solution container bottle, a photon counter and a computer.
The first flow path of the electromagnetic switching valve is connected with the outlet of the water container bottle to be detected, the second flow path and the seventh flow path are respectively connected with a waste liquid bottle, the third flow path is connected with the second interface of the quantitative ring, the fourth flow path is connected with the inlet of the mixing cavity, the sixth flow path is connected with the outlet of the spiral light-emitting tube, the ninth flow path is connected with the inlet of the carrier solution container bottle, and the tenth flow path is connected with the first interface of the quantitative ring; the outlet of the chemical luminous reagent container bottle is connected with the inlet of the mixing cavity, the outlet of the mixing cavity is connected with the inlet of the spiral luminous tube, and the outlet of the sodium carbonate solution container bottle is connected with the inlet of the spiral luminous tube; the photon counter is arranged on one side of the spiral light-emitting tube and is used for recording light signals in the spiral light-emitting tube; the photon counter is connected with the computer; and a chemiluminescent reagent solution is contained in the chemiluminescent reagent container bottle.
Further, the chemiluminescent reagent in the chemiluminescent reagent solution is acridinium ester (CAS: 194357-64-7); the concentration of the chemiluminescence reagent solution is 1-5 mu mol/L, and the preferable concentration is 1-2 mu mol/L; the pH value range of the chemiluminescence reagent solution is 2-4, and the preferable pH value is 3. The acridinium ester as the chemiluminescence reagent and hydrogen peroxide molecules have specific chemiluminescence reaction, and the reagent is a specific reagent for detecting hydrogen peroxide by a chemiluminescence method.
Further, a carrier solution is contained in the carrier solution container bottle, the carrier solution is deionized water, and the conductivity of the deionized water is 0.056 mu s/cm; the sodium carbonate solution container bottle is filled with a sodium carbonate solution, the concentration range of the sodium carbonate solution is 0.05-0.2M, and the preferred concentration is 0.1M.
Further, the electromagnetic switching valve adopts a liquid electromagnetic ten-way valve.
Further, the quantitative loop employs a peek tube, and the quantitative volume is 500 μ L.
Furthermore, the spiral luminous tube is made of quartz.
Further, the working voltage of the photon counter is 600-710 mV, and preferably, the working voltage is 630 mV.
Furthermore, the water body container bottle to be detected is connected with the electromagnetic switching valve through a hose and a peristaltic pump, the carrier solution container bottle is connected with the electromagnetic switching valve through a hose and a peristaltic pump, the quantitative ring is connected with the electromagnetic switching valve through a hose, the chemiluminescent reagent container bottle is connected with the mixing cavity through a hose and a peristaltic pump, the sodium carbonate solution container bottle is connected with the spiral light-emitting tube through a hose and a peristaltic pump, the electromagnetic switching valve is connected with the mixing cavity through a hose, the mixing cavity is connected with the spiral light-emitting tube through a hose, and the electromagnetic switching valve is connected with the waste liquid bottle through a hose; the peristaltic pump is an eight-channel peristaltic pump, the flow rate range of the peristaltic pump is 2.0-3.5 mL/min, and the preferred flow rate is 2.8 mL/min.
Furthermore, the photon counter is connected with a computer through a USB data line, and integration software origin8.5 is installed on the computer.
The invention also relates to a detection method of the device for detecting the concentration of the trace hydrogen peroxide in the surface water by adopting the chemiluminescence reagent, which comprises the following steps:
(1) under the drive of the peristaltic pump, a water body sample to be detected in a water body container bottle to be detected enters the electromagnetic switching valve; when the water body sample to be detected enters the quantitative ring and is filled with the quantitative ring, the electromagnetic switching valve switches the flow path, so that the redundant water body sample to be detected flows into the waste liquid bottle through the electromagnetic switching valve; the carrier solution conveys the water body sample to be detected in the quantitative ring to the mixing cavity through the electromagnetic switching valve.
Specifically, under the drive of a peristaltic pump, a water body sample to be detected in a water body container bottle to be detected enters an electromagnetic switching valve. At this time, the first flow path and the tenth flow path of the electromagnetic switching valve are in a communication state, the ninth flow path, the eighth flow path, the fifth flow path and the fourth flow path are in a communication state, the sixth flow path and the seventh flow path are in a communication state, and the third flow path and the second flow path are in a communication state. When the water body sample to be detected enters the quantitative ring and fills the quantitative ring, the electromagnetic switching valve switches the flow path, so that the first flow path and the second flow path are in a communication state, the ninth flow path and the tenth flow path are in a communication state, and the third flow path and the fourth flow path are in a communication state. And then the redundant water body sample to be detected directly enters the flow path II from the flow path I of the electromagnetic switching valve and then flows into the waste liquid bottle. The carrier solution conveys the water body sample to be detected in the quantitative ring to the four positions of the flow paths through the nine and ten flow paths of the electromagnetic switching valve, flows out of the electromagnetic switching valve and then enters the mixed cavity to react with the luminescent reagent.
(2) Under the drive of the peristaltic pump, a luminous reagent acridinium ester reagent in the chemiluminescent reagent container bottle enters a mixing cavity to be mixed with a water body sample to be detected, and the luminous reagent and the water body to be detected are uniformly mixed in the mixing cavity and then are conveyed into a spiral light-emitting tube.
(3) Under the drive of a peristaltic pump, a sodium carbonate solution in a sodium carbonate solution container bottle enters a spiral light-emitting tube, the pH value of a mixed solution in the spiral light-emitting tube is adjusted to be an alkaline condition, and a water body sample to be detected containing hydrogen peroxide, an acridinium ester reagent and the sodium carbonate solution react in the spiral light-emitting tube to generate a light signal.
(4) The photon counter collects the light signal in the spiral luminous tube and transmits the light signal to the computer.
(5) And the computer obtains the concentration of hydrogen peroxide in the water body to be measured through fitting according to the change process of the optical signal.
The invention has the advantages that:
(1) the invention establishes the method and the device for detecting the trace concentration of the hydrogen peroxide in the environmental water body by using the chemiluminescence method for the first time based on the chemical reaction mechanism of the azidine ester and the hydrogen peroxide, and fills the gap of the current method for measuring the hydrogen peroxide in the surface water in China. The hydrogen peroxide detection device provided by the invention has high sensitivity (the lower limit of measurement is 10)-9mol/L) and is not interfered by impurities (metal ions and dissolved organic matters) in the water body. The method adopts a chemiluminescent reagent acridinium ester to react with a trace amount of hydrogen peroxide in surface water to generate an optical signal of 470nm, and integrates the area of the optical signal to obtain the hydrogen peroxide concentration in the surface water. The chemiluminescent reagent acridinium ester adopted by the invention is a specific reagent for hydrogen peroxide detection, has specific selectivity on hydrogen peroxide, and reduces the interference of other impurities in the environment on the detection result.
(2) The invention adopts the peristaltic pump to directly mix and detect the water body and the chemiluminescent reagent, and has simple operation process. The device has the characteristics of small volume, convenience in carrying, easiness in operation and the like, can be used for detecting samples on site, can directly measure the content of superoxide radical ions in the environmental water body without a complex pretreatment process, has the advantage of portability and quick measurement compared with the conventional hydrogen peroxide measuring method, is suitable for industrial application, and has wide application prospect on treatment and scientific research of natural water bodies, and the detection process consumes very little time (less than 5 minutes).
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 shows H at various concentrations2O2(ii) a generated chemiluminescence signal profile;
FIG. 3 is a response curve of hydrogen peroxide concentration and luminescence signal integral area, which is a zero-crossing forced by linear fitting and has a slope of 43.4 μ M-1counts, correlation coefficient 0.99.
Wherein:
1. the device comprises a quantitative ring, 2, a hose, 3, a peristaltic pump, 4, a water body container bottle to be detected, 5, a carrier solution container bottle, 6, an electromagnetic switching valve, 7, a chemiluminescent reagent container bottle, 8, a sodium carbonate solution container bottle, 9, a spiral light-emitting tube, 10, a photon counter, 11, a USB data line, 12, a computer, 13, a mixing cavity, 14 and a waste liquid bottle.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
the device for detecting the concentration of trace hydrogen peroxide in surface water by using a chemiluminescent reagent as shown in fig. 1 comprises a water body container bottle to be detected 4, a carrier solution container bottle 5, an electromagnetic switching valve 6, a quantitative ring 1 (the volume of a sample to be detected is quantitatively weighed to ensure the reliability and repeatability of the detection), a mixing cavity 13, a spiral light-emitting tube 9, a chemiluminescent reagent container bottle 7, a sodium carbonate solution container bottle 8, a photon counter 10 and a computer 12. The quantitative ring is used for quantitatively intercepting the water body sample to be measured with constant volume, and the reliability and repeatability of measurement are ensured. And the electromagnetic switching valve 6 is used for switching the flow path after the quantitative ring is filled with the sample solution to be detected, so that the carrier solution flushes the sample to be detected in the quantitative ring into the mixing cavity. The carrier solution pushes the solution to be detected with constant volume in the quantitative ring into the mixing cavity through the electromagnetic switching valve to be uniformly mixed with the luminescent reagent, then the mixed solution enters the spiral light-emitting tube to be mixed with the sodium carbonate, and the hydrogen peroxide in the solution to be detected and the luminescent reagent are promoted to generate a chemical luminescence signal under the alkaline condition. The mixing cavity 13 enables the luminescent reagent and the water body sample to be detected to be uniformly mixed.
The electromagnetic switching valve 6 has a first flow path connected to the outlet of the water container bottle 4 to be tested, a second flow path and a seventh flow path connected to the waste liquid bottle 14, a third flow path connected to the interface II of the quantitative ring 1, a fourth flow path connected to the inlet of the mixing cavity, a sixth flow path connected to the outlet of the spiral light emitting tube 9, a ninth flow path connected to the inlet of the carrier solution container bottle 5, and a tenth flow path connected to the interface I of the quantitative ring 1. The outlet of the chemical luminous reagent bottle 7 is connected with the inlet of the mixing cavity, the outlet of the mixing cavity is connected with the inlet of the spiral luminous tube 9, and the outlet of the sodium carbonate solution bottle 8 is connected with the inlet of the spiral luminous tube 9. The photon counter 10 is arranged on one side of the spiral luminous tube 9 and is used for recording light signals in the spiral luminous tube 9. The probe of the photon counter 10 is arranged in alignment with the spiral luminous tube 9. In the spiral light-emitting tube, the super hydrogen peroxide in the water body to be detected reacts with a chemical luminous reagent to emit a light signal, the light signal is recorded by a photon counter 10 arranged at the front end of the spiral light-emitting tube, data recorded by the photon counter 10 is transmitted into a computer 12 through a USB data line 11, and the concentration of the hydrogen peroxide in the water body to be detected is obtained through integral fitting of integral software on the computer 12.
Further, a chemiluminescent reagent solution is contained in the chemiluminescent reagent container bottle 7. The chemiluminescent reagent in the chemiluminescent reagent solution is acridinium ester (CAS: 194357-64-7). The concentration of the chemiluminescence reagent solution is 1-5 mu mol/L, and the preferable concentration is 1-2 mu mol/L; the pH value range of the chemiluminescence reagent solution is 2-4, and the preferable pH value is 3. The acridinium ester as the chemiluminescence reagent and hydrogen peroxide molecules have specific chemiluminescence reaction, and the reagent is a specific reagent for detecting hydrogen peroxide by a chemiluminescence method. Research shows that the accuracy of the detection result of the concentration of hydrogen peroxide in the water body is obviously influenced by the selection of the chemiluminescence reagent. The chemiluminescence reagent has specific selectivity to hydrogen peroxide, and the selection of a specific chemiluminescence reagent in the process of detecting trace hydrogen peroxide in surface water based on the chemiluminescence reagent requires creative work of a person skilled in the art, and the detection result is obviously influenced by selecting different chemiluminescence reagents.
Further, a carrier solution is contained in the carrier solution container bottle 5, wherein the carrier solution is deionized water, and the conductivity of the deionized water is 0.056 mus/cm; the sodium carbonate solution container bottle is filled with a sodium carbonate solution, the concentration range of the sodium carbonate solution is 0.05-0.2M, and the preferred concentration is 0.1M.
Further, the electromagnetic switching valve 6 adopts a liquid electromagnetic ten-way valve.
Further, the quantitative loop 1 employs a peek tube, and the quantitative volume thereof is 500. mu.L.
Further, the spiral light emitting tube 9 is made of quartz.
Further, the working voltage of the photon counter 10 is 600 to 710mV, and preferably, the working voltage is 630 mV.
Further, the water body container bottle 4 to be detected is connected with the electromagnetic switching valve 6 through a hose 2 and a peristaltic pump 3, the carrier solution container bottle 5 is connected with the electromagnetic switching valve 6 through a hose and a peristaltic pump, the quantitative ring 1 is connected with the electromagnetic switching valve through a hose, the chemiluminescent reagent container bottle 7 is connected with the mixing cavity through a hose and a peristaltic pump, the sodium carbonate solution container bottle 8 is connected with the spiral light-emitting tube 9 through a hose and a peristaltic pump, the electromagnetic switching valve 6 is connected with the mixing cavity through a hose, the mixing cavity is connected with the spiral light-emitting tube 9 through a hose, and the electromagnetic switching valve 6 is connected with the waste liquid bottle 14 through a hose; the peristaltic pump 3 is an eight-channel peristaltic pump, the flow rate range of the peristaltic pump is 2.0-3.5 mL/min, and the preferred flow rate is 2.8 mL/min.
Further, the photon counter 10 is connected to a computer 12 through a USB data line 11. The computer 12 is provided with integration software origin8.5.
The process for quantitatively detecting the concentration of the trace hydrogen peroxide in the surface water by adopting the device provided by the invention comprises the following steps:
and introducing the water body sample containing hydrogen peroxide in the water body container bottle to be detected into the quantitative ring through the electromagnetic switching valve, quantitatively intercepting by the quantitative ring, and discharging the redundant water body sample to be detected into the waste liquid bottle 14. Under the drive of the peristaltic pump, the water sample solution containing hydrogen peroxide quantitatively intercepted by the quantitative loop is pushed into the mixing cavity 13 by the carrier solution and then enters the spiral light-emitting tube 9. Under the drive of the peristaltic pump, the sodium carbonate solution enters the spiral light-emitting tube 9, and the sodium carbonate solution and the carrier solution in the carrier solution container bottle 5 with the surface water sample to be detected are uniformly mixed in the spiral light-emitting tube 9 to generate a chemiluminescent signal. A photon counter 10 is adopted to detect an optical signal generated by the reaction of hydrogen peroxide in a carrier solution and a chemiluminescent reagent acridinium ester, the detection signal is converted and then recorded by software on a computer 12, the signal area is fitted by integration software, and the concentration of the hydrogen peroxide in the water body to be detected is obtained according to the signal area. After the detection is finished, the mixed liquid in the spiral light-emitting tube is discharged as waste liquid under the drive of the peristaltic pump.
The chemiluminescence method for measuring the concentration of hydrogen peroxide utilizes luminescent reagents acridinium ester and H2O2Conjugate base (HO) of2 -pKa 11.6). Acridinium esters with H starting with sodium carbonate as buffer (pH adjusted to 10-11 with NaOH)2O2The chemiluminescent reaction of (1). In the sample analysis, the pH of the acridinium ester reagent solution is adjusted to 3 to inhibit the hydrolysis of acridinium ester. The acridinium ester reagent-sample mixture to be detected enters a spiral luminescent tube 9 positioned at the front end of a photon counter 10 through a mixing loop, is mixed with a carbonate (sodium carbonate solution) buffer solution, and emits fluorescence at 470 nm. After mixing an alkaline buffer solution in an acridinium ester reagent solution, pH>At 9, the acridinium ester molecule can generate ester fast hydrolysis reaction, and the chemiluminescence signal shows first-order attenuation. The intensity of the photon signal generated by this process varies with H2O2The concentration increases. The invention can quickly detect the trace H in water based on the chemiluminescence method2O2The method has the advantages of simple operation, high sensitivity, small equipment investment, convenient carrying, wide application range and the like.
When the device is used for detecting the concentration of hydrogen peroxide in surface water, the working voltage of the photon counter is adjusted to 630mV, and the signal recording time is 1 minute. The light signal generated by hydrogen peroxide and the acridinium ester as a chemical luminous reagent acts on a photoresistor of a photon counter and is converted into an electric signal through a multiplier tube to be input into a computer. The concentration of hydrogen peroxide in surface water can be converted by integrating the area of the chemiluminescence signal.
In order to understand the effect of the device and the method for detecting the concentration of the trace hydrogen peroxide in the surface water, super hydrogen peroxide solution samples with the concentrations of 0.05 mu mol/L, 0.1 mu mol/L, 0.13 mu mol/L, 0.26 mu mol/L, 0.52 mu mol/L and 0.77 mu mol/L are prepared, and the fact that the hydrogen peroxide concentration in the concentration range (the pH value is 7) has a good linear relation with a detection signal and the correlation coefficient is 0.99 shows that the hydrogen peroxide concentration and a luminescence signal have extremely strong response correlation, so that the hydrogen peroxide measuring method is feasible. The ratio between the hydrogen peroxide concentration and the signal units (counts) was 43400counts/μmol (see FIGS. 2 and 3). In addition, the analysis and research on the influence of the type and concentration of the chemiluminescence reagent, the pH value and the working voltage of the photon counter on the detection effect are carried out, and the following results are obtained:
influence of one or more chemiluminescent reagents on the detection
Setting the experimental conditions: the working voltage of the photon counter is 630mV, the flow rate of the peristaltic pump is 2.8mL/min, the concentration of the chemiluminescent reagent is 1 mu mol/L, and the pH value of the chemiluminescent reagent solution is 3. Under the condition, the chemiluminescence reagents 2-methyl-6- (4-methylphenyl) -3, 7-dihydroimidazo [1,2-A ] pyrazine-3-one hydrochloric acid (MCLA, CAS:128322-44-1), luminol chemiluminescence reagent (CAS number: 521-31-3) and acridinium ester chemiluminescence reagent (CAS number: 194357-64-7) are used for making a standard curve for the concentration of the series of hydrogen peroxide, and the obtained linear correlation coefficients are 0.06, 0.86 and 0.99 respectively. Although the luminol chemical reagent also shows the chemiluminescence characteristic to hydrogen peroxide, when iron ions exist in a range of 1-5 mu mol/L, the linear correlation coefficient is reduced to 0.24, and acridinium ester is not affected. Therefore, the acridinium chemiluminescent reagent is a specific and stable luminescent reagent for detecting hydrogen peroxide.
Secondly, the influence of the concentration of the acridinium ester serving as a chemiluminescent reagent on the detection effect
Setting the experimental conditions: the working voltage of a photon counter is 630mV, the flow rate is 2.8mL/min, the pH value of the acridinium ester reagent solution is 3, under the condition, the acridinium ester concentration is 0.5 mu mol/L, 1 mu mol/L and 2 mu mol/L respectively make standard curves for the series of hydrogen peroxide concentrations, and the linear correlation coefficients are 0.92, 0.99 and 0.95 respectively. The experimental result shows that the acridinium ester has the best response relation when the concentration is 1 mu mol/L, and the detection effect is the best.
Influence of pH value of acridinium ester solution on detection of hydrogen peroxide concentration by chemiluminescence method
Setting conditions: the working voltage of a photon counter is 630mV, the flow rate is 2.8mL/min, the concentration of the chemiluminescent reagent acridinium ester is 1 mu mol/L, and under the condition, the water bodies with the pH values of 2, 3 and 4 and containing the hydrogen peroxide concentration are respectively detected. The correlation coefficients of the standard curve between the hydrogen peroxide concentration and the signal are 0.88, 0.99 and 0.84 respectively. The experimental result shows that the pH value is 3, the best response relation is realized, and the detection effect is best.
Fourthly, the influence of different working voltages of the photon counter on the detection of the concentration of hydrogen peroxide by the chemiluminescence method
Setting the test conditions: the influence of the voltages of the multiplier tube of the photon counter of 600mV, 630mV, 680mV and 710mV on the detection of hydrogen peroxide by a chemiluminescence method is discussed under the condition that the flow rate of a peristaltic pump is 2.8mL/min, the concentration of the acridinium ester serving as a chemiluminescent reagent is 1 mu mol/L and the pH of a solution of the acridinium ester luminescent reagent is 6. Under the condition, the voltage of 600mV can not detect the hydrogen peroxide with the concentration range less than 0.2 mu mol/L. At other test voltages, the correlation coefficients of the standard curves were 0.99, 0.99 and 0.98, respectively. Experimental results show that the photon counter has the best response relation when the voltage is 680mV, and the detection effect is the best.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. Adopt the device of chemiluminescence reagent detection surface aquatic trace hydrogen peroxide concentration, its characterized in that: comprises a water body container bottle to be measured, a carrier solution container bottle, an electromagnetic switching valve, a quantitative ring, a mixing cavity, a spiral light-emitting tube, a chemiluminescent reagent container bottle, a sodium carbonate solution container bottle, a photon counter and a computer;
the first flow path of the electromagnetic switching valve is connected with the outlet of the water container bottle to be detected, the second flow path and the seventh flow path are respectively connected with a waste liquid bottle, the third flow path is connected with the second interface of the quantitative ring, the fourth flow path is connected with the inlet of the mixing cavity, the sixth flow path is connected with the outlet of the spiral light-emitting tube, the ninth flow path is connected with the inlet of the carrier solution container bottle, and the tenth flow path is connected with the first interface of the quantitative ring; the outlet of the chemical luminous reagent container bottle is connected with the inlet of the mixing cavity, the outlet of the mixing cavity is connected with the inlet of the spiral luminous tube, and the outlet of the sodium carbonate solution container bottle is connected with the inlet of the spiral luminous tube; the photon counter is arranged on one side of the spiral light-emitting tube and is used for recording light signals in the spiral light-emitting tube; the photon counter is connected with the computer; and a chemiluminescent reagent solution is contained in the chemiluminescent reagent container bottle.
2. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the chemiluminescent reagent in the chemiluminescent reagent solution is acridinium ester (CAS: 194357-64-7); the concentration of the chemiluminescence reagent solution is 1-5 mu mol/L; the pH value range of the chemiluminescence reagent solution is 2-4.
3. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the carrier solution is contained in the carrier solution container bottle, the carrier solution is deionized water, and the conductivity of the carrier solution is 0.056 mu s/cm; the sodium carbonate solution is contained in the sodium carbonate solution container bottle, and the concentration range of the sodium carbonate solution is 0.05-0.2M.
4. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the electromagnetic switching valve adopts a liquid electromagnetic ten-way valve.
5. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the quantification loop is a peek tube, and the quantification volume is 500 mu L.
6. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the spiral luminous tube is made of quartz.
7. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the working voltage of the photon counter is 600-710 mV.
8. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the device comprises a carrier solution container bottle, a quantitative ring, a chemical luminous reagent container bottle, a mixing cavity, a sodium carbonate solution container bottle, a waste liquid bottle, an electromagnetic switching valve, a hose, a peristaltic pump, a hose, a peristaltic pump, a hose; the peristaltic pump is an eight-channel peristaltic pump, and the flow rate range of the peristaltic pump is 2.0-3.5 mL/min.
9. The device for detecting the concentration of trace hydrogen peroxide in surface water by using the chemiluminescent reagent according to claim 1, wherein the device comprises: the photon counter is connected with a computer through a USB data line, and integration software origin8.5 is installed on the computer.
10. The method for detecting the concentration of the trace hydrogen peroxide in the surface water by using the chemiluminescent reagent according to any one of claims 1 to 9, comprising the following steps:
(1) under the drive of the peristaltic pump, a water body sample to be detected in a water body container bottle to be detected enters the electromagnetic switching valve; when the water body sample to be detected enters the quantitative ring and is filled with the quantitative ring, the electromagnetic switching valve switches the flow path, so that the redundant water body sample to be detected flows into the waste liquid bottle through the electromagnetic switching valve; the carrier solution conveys the water body sample to be detected in the quantitative ring to the mixed cavity through the electromagnetic switching valve;
(2) under the drive of a peristaltic pump, a luminescent reagent acridinium ester reagent in a chemiluminescent reagent container bottle enters a mixing cavity to be mixed with a water body sample to be detected, and the luminescent reagent and the water body to be detected are uniformly mixed in the mixing cavity and then are conveyed into a spiral light-emitting tube;
(3) under the drive of a peristaltic pump, the sodium carbonate solution in the sodium carbonate solution container bottle enters a spiral light-emitting tube, and the pH value of the mixed solution in the spiral light-emitting tube is adjusted to be in an alkaline condition; reacting a water body sample to be detected containing hydrogen peroxide, an acridinium ester reagent and a sodium carbonate solution in a spiral light-emitting tube to generate an optical signal;
(4) the photon counter collects the optical signal in the spiral luminous tube and transmits the optical signal to the computer;
(5) and the computer obtains the concentration of hydrogen peroxide in the water body to be measured through fitting according to the change process of the optical signal.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07159407A (en) * | 1993-12-06 | 1995-06-23 | Olympus Optical Co Ltd | Optical immunoassay method and immunoassay apparatus used therefor |
| US6673560B1 (en) * | 1998-11-25 | 2004-01-06 | Bayer Corporation | Measurement of hydride using chemiluminescent acridinium compounds and applications thereof |
| CN101865912A (en) * | 2009-04-14 | 2010-10-20 | 南京大学 | Fast chemiluminescence immune detection system and analysis method |
| CN102788782A (en) * | 2012-08-15 | 2012-11-21 | 山东省科学院海洋仪器仪表研究所 | Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode |
| CN106018386A (en) * | 2016-04-20 | 2016-10-12 | 杭州大茗堂生物科技有限公司 | Analytical method of antioxidant capacity in tea or tea products |
| CN109211883A (en) * | 2017-07-03 | 2019-01-15 | 苏州长光华医生物医学工程有限公司 | The chemiluminometry of concentration of hydrogen peroxide in a kind of detection solution |
-
2020
- 2020-09-04 CN CN202010919028.0A patent/CN112268896A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07159407A (en) * | 1993-12-06 | 1995-06-23 | Olympus Optical Co Ltd | Optical immunoassay method and immunoassay apparatus used therefor |
| US6673560B1 (en) * | 1998-11-25 | 2004-01-06 | Bayer Corporation | Measurement of hydride using chemiluminescent acridinium compounds and applications thereof |
| CN101865912A (en) * | 2009-04-14 | 2010-10-20 | 南京大学 | Fast chemiluminescence immune detection system and analysis method |
| CN102788782A (en) * | 2012-08-15 | 2012-11-21 | 山东省科学院海洋仪器仪表研究所 | Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode |
| CN106018386A (en) * | 2016-04-20 | 2016-10-12 | 杭州大茗堂生物科技有限公司 | Analytical method of antioxidant capacity in tea or tea products |
| CN109211883A (en) * | 2017-07-03 | 2019-01-15 | 苏州长光华医生物医学工程有限公司 | The chemiluminometry of concentration of hydrogen peroxide in a kind of detection solution |
Non-Patent Citations (1)
| Title |
|---|
| D.WHITNEY KING ET AL.: "Flow Injection Analysis of H2O2 in Natural Waters Using Acridinium Ester Chemiluminescence: Method Development and Optimization Using a Kinetic Model", 《ANALYTICAL CHEMISTRY》 * |
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