CN112098386A - Preparation method of dissolved oxygen fluorescence sensing film and sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method - Google Patents
Preparation method of dissolved oxygen fluorescence sensing film and sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method Download PDFInfo
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Abstract
The invention discloses a preparation method of a dissolved oxygen fluorescence sensing membrane and a sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method.
Description
Technical Field
The invention belongs to the technical field of detection of dissolved oxygen in water body sediments, and particularly relates to a simple preparation method of a dissolved oxygen fluorescence sensing membrane and a sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method.
Background
Oxygen is the basis of life. It is not only essential for the survival of individual animals, but also regulates the global circulation of the main nutrients (nitrogen, phosphorus, sulfur, iron, manganese and other metallic elements) and carbon. In the ocean, at least for the past half century, the oxygen content of open ocean and coastal waters has been decreasing, primarily due to increased global temperatures and nutrient discharges into coastal waters from human activities. These changes promote microbial respiration and increase oxygen consumption, reduce oxygen solubility in water, and in addition reduce the rate of oxygen re-supply from the atmosphere to the interior of the ocean, resulting in the ocean water and sediments being anaerobic. Along with the input of a large amount of nutrients such as nitrogen, phosphorus and the like in freshwater systems such as lakes, reservoirs and the like, the problem of water eutrophication is serious, and a large amount of outbreak of cyanobacterial bloom is caused. The burst cyanobacterial bloom reduces the transparency of the water body to cause the degradation of aquatic plants, and the cyanobacterial bloom quickly exhausts oxygen in the water body in the process of decay and degradation, and also reduces oxygen in the water body and sediment. The reduction of water oxygen in lakes and oceans creates localized dead water zones, and the anaerobic nature of sediments results in the release of large amounts of endogenous nutrient salts, with a range of biological, ecological and environmental consequences. Further research into bodies of water and sediments is therefore needed to understand and predict long-term global and regional scale oxygen changes and their impact on marine and freshwater fisheries and ecosystems.
The measurement of the dissolved oxygen in the water body can use a portable dissolved oxygen meter, but because the probe of the dissolved oxygen meter is large (the minimum probe diameter is 1.2 cm, and the Raynaud magnetic DO-9585), the concentration information of the dissolved oxygen in the sediment can not be obtained in situ. The current method of micro-electric level is generally used for solving the problem, the minimum tip diameter of the dissolved oxygen electrode can reach 100 mu m, and the in-situ measurement of the dissolved oxygen at the sediment-water interface can be realized. However, the micro-electrode can only obtain the dissolved oxygen profile information of one point, because the deposit has high spatial heterogeneity, the profile change information of the dissolved oxygen in the deposit cannot be really reflected, and the micro-electrode needs to be expensive from danish import (about 10000 yuan per capita of dissolved oxygen electrodes), has thin tip, is damaged immediately when the tip is touched, has long measuring time (30 min one profile), and needs to be operated by professional personnel. Therefore, it is urgently needed to invent a new method for measuring dissolved oxygen at a sediment-water interface to solve the problem. Recently developed planar optical sensors provide new approaches for the detection of dissolved oxygen in deposits, such as: chinese patent application 202010133853.8 proposes "a method for preparing an optical sensing film for detecting two-dimensional distribution of dissolved oxygen in sediment", which comprises a transparent PET substrate, a sensing layer and a protective layer, wherein the sensing layer is formed by uniformly mixing a fluorescent dye and a donor dye and then fixing the mixture on the surface of the transparent PET substrate, and the protective layer is formed by coating diluted gas permeation type silicon rubber on the sensing layer. The sensing film prepared by the method obtains an emission image of the optical sensing film through a CCD camera under the irradiation of ultraviolet exciting light, and finally obtains two-dimensional information of the concentration of dissolved oxygen in the sediment. Although the technology can effectively obtain the two-dimensional profile information of the dissolved oxygen in the sediment, the preparation process of the sensing film uses highly toxic solvents such as toluene, chloroform and the like and difficult-to-degrade materials such as polystyrene and the like, and mass production can cause certain harm to the environment and human bodies, so that the development of a simple, high-efficiency, environment-friendly and high-performance dissolved oxygen preparation method and a rapid detection method is of great importance.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the existing problems and defects, the invention aims to provide a preparation method of a dissolved oxygen fluorescence sensing membrane and a sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method.
The technical scheme is as follows: in order to realize the purpose, the invention adopts the following technical scheme: a preparation method of a fluorescence sensing film for dissolved oxygen at a sediment-water interface comprises the following steps:
(1) preparing ethanol solution containing 1-5 mg/ml of oxygen sensitive dye and 1-5 mg/ml of reference dye as dye stock solution,
(2) mixing a dye stock solution and water according to a volume ratio of 6-10: 1, adding 0.05-0.2 g/ml HydroMed D4, and stirring and dissolving to obtain a casting solution;
(3) coating the casting solution on the surface of a transparent polyester film by a blade coating or spin-coating method, and drying for more than 12 hours until the film is completely dried to obtain a sensing layer;
(4) then, continuously coating a white silicone rubber layer on the surface of the sensing layer to be used as a shading protective layer, and obtaining a dissolved oxygen sensing film;
(5) dissolved oxygen sensing film calibration: firstly, obtaining different dissolved oxygen concentrations by adjusting the gas flow of nitrogen and oxygen introduced into deionized water; then, the dissolved oxygen sensing film is pasted on the inner wall of a transparent container and then is immersed in the deionized water with different dissolved oxygen concentrations, and the fluorescent images of the sensing film under different dissolved oxygen concentrations are obtained through a CMOS camera under the irradiation of an ultraviolet excitation light source of 395 nm; then, extracting the red channel R and the green channel G of the fluorescence image under different dissolved oxygen concentrations, and calculating to obtain the fluorescence intensity ratioFR/G, and ratio of fluorescence intensity to single exponential functionFAnd carrying out curve fitting on the relation with the dissolved oxygen concentration to obtain a dissolved oxygen response model of the sensing film, wherein the formula (1):
in the formula (I), the compound is shown in the specification,a，bandF 0are fitting parameters.
Preferably, the oxygen-sensitive dye adopts PtOEP (Platinum (II) 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin) or PtTFPP; the reference dye is Coumarin 6 (Coumarin 6), Macrolex yellow or Coumarin 545T (Coumarin 545T).
Preferably, the fluorescence image of the sensing film in the step (5) is acquired by a CMOS camera under a 500nm long-pass filter.
The invention also provides a sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method based on the fluorescent sensing film, which comprises the following steps:
(1) splicing the corrected dissolved oxygen sensing film on the inner wall of the transparent organic glass tube, and putting the glass tube into a water sampling point to sample a sediment in-situ sample;
(2) introducing oxygen into the collected sediment in-situ sample water at the flow rate of 0.2-0.6L/min for aerobic culture for several days, and collecting a fluorescence image of the sensing film in a dark room;
(3) continuously introducing nitrogen into the overlying water at the flow rate of 0.2-0.6L/min, carrying out anaerobic culture for several days, and collecting a fluorescence image of the sensing film in a dark room;
(4) and finally, drawing a two-dimensional dynamic distribution diagram of the dissolved oxygen of the sediment-water interface of the obtained sediment in-situ sample under aerobic and anaerobic conditions by extracting the fluorescence intensity ratio of each point of the fluorescence image and comparing the fluorescence intensity ratio with the standard dissolved oxygen response model after correction fitting.
Preferably, the sediment height of the collected sediment in-situ sample is 20 +/-5 cm, and the height of the overlying water is 10 +/-2 cm.
Has the advantages that: compared with the prior art, the invention (1) prepares the dissolved oxygen fluorescence sensing film by using a simple and efficient method, and finally realizes the in-situ two-dimensional high-resolution detection of the dissolved oxygen at the sediment-water interface by using the fluorescence ratio imaging principle. The preparation method of the dissolved oxygen sensing film is simple and efficient, and does not need complex equipment. Compared with the traditional dissolved oxygen sensing film preparation method, the preparation method uses highly toxic solvents such as toluene, chloroform and the like and refractory materials such as polystyrene and the like; in the preparation process of the dissolved oxygen sensing membrane, the organic solvent used is ethanol, the polymer is HydroMed D4, both are nontoxic solutions/materials, and the HydroMed D4 has good gas permeability and can increase the sensitivity of the sensing membrane. The dissolved oxygen sensing film has quick reaction time (less than 10 s) and good reversibility, and the white silicon rubber coating is coated to reduce background interference and improve the stability of the sensing film. Therefore, the invention solves the problem of in-situ two-dimensional high-resolution dissolved oxygen measurement of the sediment-water interface under the conditions of simplicity, high efficiency, environmental friendliness and high performance. (2) For a long time, the determination of the dissolved oxygen of the sediment can only use a micro-electrical system of Denmark, and the imported dissolved oxygen electrode is expensive and easy to damage, thus causing inconvenience for the research of the sediment. The invention breaks through the state of monopoly abroad, improves the traditional resolution ratio from one dimension to two dimension, and provides a strong and favorable tool for comprehensively and deeply developing the research on the water-water interface of lakes, reservoirs, riverways and marine sediments.
Drawings
FIG. 1 is a schematic structural diagram of the principle of a sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method of a fluorescence sensing film according to the present invention;
FIG. 2 is a graph showing the red and green channel fluorescence intensities of the dissolved oxygen sensing film of the present invention at different dissolved oxygen concentrations;
FIG. 3 is a graph of fluorescence intensity ratio versus dissolved oxygen response for a dissolved oxygen sensing film according to an embodiment of the present invention at different dissolved oxygen concentrations;
FIG. 4 is a graphical representation of a two-dimensional dynamic change of dissolved oxygen at the sediment-water interface of a dissolved oxygen sensing membrane according to an embodiment of the invention under aerobic and anaerobic conditions;
FIG. 5 is a schematic diagram showing the comparison of the two-dimensional distribution information of dissolved oxygen of root sediments obtained by the oxygen-dissolving sensing film in the embodiment of the present invention at the 5 th day and the 10 th day of the growth of tape grass.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
The invention further discloses a rapid detection method for two-dimensional high-resolution dissolved oxygen dynamic change of a sediment-water interface and a working principle thereof by combining the attached drawing.
Referring to fig. 1, a method for rapidly detecting dynamic change of two-dimensional high-resolution dissolved oxygen at a sediment-water interface comprises a transparent polymethyl methacrylate organic glass tube for collecting sediment, a black light shading plate, a plane optical pole of a dissolved oxygen sensing film, an excitation light source, an optical filter, a CMOS camera and a computer. The sampling tube contains sediment and overlying water.
(1) Firstly, dissolving an oxygen sensitive dye PtOEP and a reference dye Coumarin 6 for preparing a fluorescent sensing film in ethanol to obtain a dye stock solution (the concentration of the PtOEP and the Coumarin 6 is 1-5 mg/ml); HydroMed D4 was added to a volume ratio of 9: 1, stirring and dissolving the mixed solution of the dye stock solution and water to obtain a casting solution (the concentration of HydroMed D4 is 0.05-0.1 g/ml); coating the casting solution on the surface of a transparent polyester film by using a blade coating or spin coating method, and drying for at least 12 h; and after the sensing layer is completely dried, coating white silicon rubber on the surface of the sensing layer to serve as a light shielding layer and a protective layer, and drying for at least 24 hours to finally prepare the dissolved oxygen sensing film.
(2) The prepared dissolved oxygen sensing film is attached to the inner wall of a rectangular transparent polymethyl methacrylate organic glass container filled with deionized water with different dissolved oxygen concentrations. And (3) irradiating the sensing film by using an ultraviolet excitation light source of 395 nm, and finally acquiring fluorescent images of the sensing film under different oxygen concentrations by using a CMOS camera and combining a long-pass filter of 500 nm. Extracting red channel R and green channel G of the fluorescence image of the sensing film under different dissolved oxygen concentrations, as shown in FIG. 2, calculating the fluorescence intensity ratio of the two channelsFAnd (3) performing curve fitting by using a single exponential fitting equation to obtain a response curve of the sensing film to the dissolved oxygen:
in the formula (II)CIs the concentration of dissolved oxygen;a，bandF 0are fitting parameters. The response curve of the composite fluorescent sensing film to dissolved oxygen is shown in fig. 3, and a calibration curve is finally obtained:
(3) flatly attaching the calibrated dissolved oxygen sensing film to the inner wall of a transparent polymethyl methacrylate organic glass tube (recommended size is 30 cm in height and the inner diameter is 9 cm) to avoid light and bring the dissolved oxygen sensing film to a sampling point of the Taihu lake, collecting a deposit in-situ sample (about 20 cm of deposit and 10 cm of overlying water), quickly transporting the deposit in-situ sample back to a laboratory in a light-avoiding manner, slowly filling oxygen into the overlying water at a flow rate of 0.4L/min, and moving the organic glass box to a dark room after aerobic culture is stabilized to obtain a fluorescence image. Then, the oxygen is changed into nitrogen, the flow of the nitrogen is 0.4L/min, and the organic glass box is moved to a darkroom to obtain a fluorescence image after 3 days of anaerobic culture stabilization. According to the method, the two-dimensional dynamic distribution of the dissolved oxygen at the aerobic and anaerobic sediment-water interface can be obtained after calculation and mapping, and is shown in figure 4. The result shows that the dissolved oxygen concentration values of the overlying water and the sediments are obviously increased in an aerobic manner, and are obviously reduced in an anaerobic manner, the dissolved oxygen of the overlying water is 250 mu M under the aerobic condition, and the dissolved oxygen of the overlying water is reduced to 0 mu M under the anaerobic condition.
(4) Similar to (3), the polymethyl methacrylate organic glass tube attached by the sensing film of dissolved oxygen is taken to a sampling point of the Taihu lake in a dark place, and the sediment in-situ sample is collected and then quickly transported back to the laboratory in a dark place. Planting eel grass seedlings in the sediments, inclining the columns attached with the sensing films to the ground at 45 ℃ to enable eel grass roots to grow attached with the films under the action of gravity, and moving the organic glass box to a darkroom to acquire fluorescence images after 5 days and 10 days of growth of the eel grass seedlings respectively. According to the method, the two-dimensional dynamic distribution of the dissolved oxygen of the sediments around the roots of the tape grass can be obtained after calculation and drawing. The results show that the dissolved oxygen concentration of the sediment around the root system is obviously higher than that of the sediment in the non-root system area due to the oxygen secretion of the root system, and the dissolved oxygen of the sediment around the root system is higher than that of the sediment around the root system on the 5 th day of the growth of the tape grass, as shown in figure 5.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of a fluorescence sensing film for dissolved oxygen at a sediment-water interface comprises the following steps:
(1) preparing ethanol solution containing 1-5 mg/ml of oxygen sensitive dye and 1-5 mg/ml of reference dye as dye stock solution,
(2) mixing a dye stock solution and water according to a volume ratio of 6-10: 1, adding 0.05-0.2 g/ml HydroMed D4, and stirring and dissolving to obtain a casting solution;
(3) coating the casting solution on the surface of a transparent polyester film by a blade coating or spin-coating method, and drying for more than 12 hours until the film is completely dried to obtain a sensing layer;
(4) then, continuously coating a white silicone rubber layer on the surface of the sensing layer to be used as a shading protective layer, and obtaining a dissolved oxygen sensing film;
(5) dissolved oxygen sensing film calibration: firstly, obtaining different dissolved oxygen concentrations by adjusting the gas flow of nitrogen and oxygen introduced into deionized water; then, the dissolved oxygen sensing film is pasted on the inner wall of a transparent container and then is immersed in the deionized water with different dissolved oxygen concentrations, and the fluorescent images of the sensing film under different dissolved oxygen concentrations are obtained through a CMOS camera under the irradiation of an ultraviolet excitation light source of 395 nm; then, extracting the red channel R and the green channel G of the fluorescence image under different dissolved oxygen concentrations, and calculating to obtain the fluorescence intensity ratioFR/G, and ratio of fluorescence intensity to single exponential functionFAnd carrying out curve fitting on the relation with the dissolved oxygen concentration to obtain a dissolved oxygen response model of the sensing film, wherein the formula (1):
in the formula (I), the compound is shown in the specification,a，bandF 0are fitting parameters.
2. The method for preparing a fluorescence sensing film for sediment-water interface dissolved oxygen according to claim 1, wherein the method comprises the following steps: the oxygen sensitive dye adopts PtOEP or PtTFPP; the reference dye adopts Coumarin 6, Macrolex yellow or Coumarin 545T.
3. The method for preparing a fluorescence sensing film for sediment-water interface dissolved oxygen according to claim 1, wherein the method comprises the following steps: and (5) collecting the fluorescent image of the sensing film under a 500nm long-pass filter by a CMOS camera.
4. A sediment-water interface dissolved oxygen two-dimensional dynamic distribution detection method based on the fluorescent sensing film of any one of claims 1 to 3 is characterized by comprising the following steps:
(1) splicing the corrected dissolved oxygen sensing film on the inner wall of the transparent organic glass tube, and putting the glass tube into a water sampling point to sample a sediment in-situ sample;
(2) introducing oxygen into the collected sediment in-situ sample water at the flow rate of 0.2-0.6L/min for aerobic culture for several days, and collecting a fluorescence image of the sensing film in a dark room;
(3) continuously introducing nitrogen into the overlying water at the flow rate of 0.2-0.6L/min, carrying out anaerobic culture for several days, and collecting a fluorescence image of the sensing film in a dark room;
(4) and finally, drawing a two-dimensional dynamic distribution diagram of the dissolved oxygen of the sediment-water interface of the obtained sediment in-situ sample under aerobic and anaerobic conditions by extracting the fluorescence intensity ratio of each point of the fluorescence image and comparing the fluorescence intensity ratio with the standard dissolved oxygen response model after correction fitting.
5. The method for detecting two-dimensional dynamic distribution of dissolved oxygen at a sediment-water interface of a fluorescent sensing film according to claim 4, wherein the method comprises the following steps: the sediment height of the collected sediment in-situ sample is 20 +/-5 cm, and the height of the overlying water is 10 +/-2 cm.
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| CN116067843A (en) * | 2023-02-03 | 2023-05-05 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Sediment water interface pollutant migration conversion and oxygen balance mechanism simulation device |
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