CN114018964A - Method for detecting degradation of tetracycline organic pollutant wastewater based on in-situ high-field nuclear magnetic resonance technology - Google Patents
Method for detecting degradation of tetracycline organic pollutant wastewater based on in-situ high-field nuclear magnetic resonance technology Download PDFInfo
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Abstract
The invention discloses a method for detecting degradation of tetracycline organic pollutant wastewater based on an in-situ high-field nuclear magnetic resonance technology1H signal, in-situ real-time monitoring chemical structure change of the tetracycline organic pollutants caused by photocatalytic degradation, and performing integral processing on content signal data in a spectrogram to quickly detect the concentration reduction of the tetracycline organic pollutants and the condition of degradation products so as to represent the real degradation process and efficiency of the tetracycline organic pollutants. The method is simple to operate, high in accuracy and capable of detecting the degradation degree of colorless toxic groups, and does not need to pretreat the original solution or separate products. The method is expected to be popularized in the aspect of removing other organic pollutants, particularly monitoring colorless organic pollutants.
Description
Technical Field
The invention belongs to the technical field of nuclear magnetic resonance, relates to detection of a water treatment detection technology, and particularly relates to a method for detecting degradation of tetracycline organic pollutant wastewater by an in-situ nuclear magnetic resonance technology.
Background
Antibiotics are widely used in veterinary and aquaculture to control disease and promote growth. After excretion or disposal of expired drugs, it is inevitable that more and more of these antibiotics will eventually be present in water and soil. Tetracycline (TC) is the second favored antibiotic in terms of production and use, and has been widely used in livestock feed and disease control for decades. Tetracycline is not biodegradable during conventional water treatment and can hinder the removal of other organic contaminants. Therefore, degradation of tetracycline is an important task for scientists. The photocatalytic technology is recognized as a pollution-free, effective and clean method, solar energy can be converted and stored into chemical energy through a chemical catalysis method, and environmental pollution is reduced, so that the degradation of tetracycline through a photocatalytic reduction process has important research significance.
Currently, numerous methods have been developed to determine the efficiency of tetracycline degradation, including high performance liquid chromatography, ultraviolet-visible spectrophotometry, and the like. Among these detection methods, ultraviolet-visible spectrophotometry has attracted much attention. The ultraviolet-visible spectrophotometry is an analysis method established based on the difference of selective absorption of light by substance solutions. It has the characteristics of low cost and high detection speed. However, in the case of ultraviolet-visible spectrophotometry, separation of the liquid/powder catalyst is required, and it is difficult to separate different chromophoric groups by absorption in the same wavelength band. Furthermore, if the toxic group becomes colorless before complete degradation, this will greatly affect the accuracy of the results. That is, uv-vis spectrophotometry has a stronger dependence on the absorbance of the group. Therefore, the development of a method which is rapid, simple and accurate and can quantify the degradation degree of TC without pretreatment has important value for evaluating the photocatalytic degradation process of TC.
The nuclear magnetic resonance spectrum is one of the important characterization techniques of material structure and performance, and each tetracycline molecular structure contains1The structural content of H can be measured by nmr techniques. At present, no report for detecting the degradation of the tetracycline organic pollutant wastewater by using an in-situ nuclear magnetic resonance detection technology exists.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the method for detecting the degradation of the tetracycline organic pollutant wastewater by using the in-situ high-field liquid nuclear magnetic resonance technology, which is quick, simple and accurate, and can realize the quantitative detection of the degradation of the organic pollutants without carrying out pretreatment to separate products. The in-situ liquid nuclear magnetic resonance method adopted by the invention can detect the degradation efficiency of the tetracycline organic pollutant wastewater, can realize real-time monitoring of the structure change process of the tetracycline organic pollutant under the in-situ illumination condition, and can quickly detect the conditions of the concentration reduction and degradation products of the tetracycline organic pollutant, thereby representing the degradation efficiency of the tetracycline organic pollutant. The method has the advantages of rapidness, real-time property and no need of pretreatment, and can detect the colorless group.
The invention provides a novel method for quantitatively detecting degradation of organic pollutants in chemical reaction based on an in-situ high-field nuclear magnetic resonance technology1H signal, in-situ real-time monitoring chemical structure change of the tetracycline organic pollutants caused by photocatalytic degradation, and performing integral processing on content signal data in a spectrogram to quickly detect the concentration reduction of the tetracycline organic pollutants and the condition of degradation products so as to represent the real degradation process and efficiency of the tetracycline organic pollutants. The method comprises the following specific steps:
step (1): adding the suspension containing the catalyst powder and the tetracycline organic pollutant solution into a matched nuclear magnetic tube, and performing ultrasonic homogenization;
step (2): assembling in-situ light source equipment, putting the nuclear magnetic tube filled with the sample to be detected into a cavity of a liquid high-field nuclear magnetic resonance spectrometer, and introducing light into the nuclear magnetic tube through an optical fiber;
and (3): excitation in a sample using a single pulse sequence1H signal, of tetracycline organic pollutants1H signal changes with illumination time and is detected in situ;
and (4): obtained by in-situ detection of different illumination time in the step (3)1Performing integration treatment on H signal data to finally obtain tetracycline compoundsAnd (4) degradation efficiency of organic pollutants.
Compared with the existing ultraviolet-visible spectrophotometry, the method does not need to separate liquid from catalyst powder during detection, and the in-situ nuclear magnetic resonance technology can detect the structural change process of the tetracycline organic pollutants in the liquid in real time. Because the ultraviolet-visible spectrophotometry has strong dependence on the light absorption of radicals, in the reaction process, the ultraviolet spectrophotometry can only judge the reaction process according to the color of a solution from colored to colorless or the shade of the color, and cannot achieve good judgment effect on further reaction possibly occurring in the colorless solution. The method can detect toxic and colorless groups and accurately detect the reaction process in a colorless solution, so that the method can quantify the degradation degree of the tetracycline organic pollutants quickly, simply and accurately without pretreatment;
the quantification method specifically comprises the steps of carrying out integral processing on nuclear magnetic signal data obtained by in-situ detection at different illumination time, and distinguishing benzene ring structures and closely spaced benzene ring structures in the tetracycline organic pollutants through a high-field nuclear magnetic resonance experiment. The content of the tetracycline organic pollutant molecules is calculated according to the integral area, the degradation rate of the tetracycline organic pollutant can be calculated through trend reduction, meanwhile, the change condition of each chemical structure in the tetracycline organic pollutant along with illumination time is obtained according to the integral area, and finally the degradation degree of the tetracycline organic pollutant is obtained.
The method is carried out on a high-field magnetic resonance instrument, wherein the high field refers to the magnetic field intensity of more than 200M;
in the step (1), the catalyst is TiO2、10-TiO2、20-TiO2、30-TiO2、40-TiO2、50-TiO2、60-TiO2Preferably 30-TiO is selected from2、40-TiO2(ii) a The addition amount of the catalyst powder is 0.5 mg-10 mg; preferably, it is 1 mg.
In the step (1), the organic pollutants are tetracycline organic pollutants, and commonly comprise one or more of tetracycline, aureomycin and the like; preferably, it is tetracycline.
In the step (1), the volume of the solution added with the tetracycline organic pollutants is 1 mL-2 mL, preferably 1 mL; the concentration of the added organic pollutant solution is 1 mg/L-2000 mg/L, preferably 1000 mg/L. In the step (1), the diameter of the nuclear magnetic tube is preferably 5mm, and the height of the nuclear magnetic tube is preferably 100 mm.
In the step (1), the ultrasonic conditions are that the ultrasonic power is 40W, the time is 5min, the temperature is 25 ℃, and the ultrasonic frequency is 70 kHz.
The whole in-situ test process of the invention does not need product separation.
In the step (2), the in-situ light source device comprises a light source and an optical fiber; the in-situ light source equipment comprises the following assembling steps: an optical fiber bundle (composed of 5-7 optical fibers, with a total diameter of about 0.2-0.3 cm; preferably, 7 optical fibers with a diameter of 0.3cm) composed of bare fibers without metal coating is connected with a light source through a condenser.
The light source is one or more of a common xenon lamp light source, a mercury lamp light source, a metal halide lamp light source and the like; preferably, the present invention uses a general 300W xenon lamp as a light source. It is noted that the present invention has no substantial requirements for the light source and the illumination intensity.
The invention designs an optical fiber bundle consisting of bare fibers without metal wrapping, which mainly aims to avoid the interference of an optical fiber metal wrapping layer on nuclear magnetic signals, ensure the stability of illumination and avoid the condition of no light introduction caused by the damage of a single optical fiber.
The light source and the nuclear magnetic tube are connected by the optical fiber.
In the step (2), the optical fiber is a customized metal-free wrapped optical fiber bundle.
In the step (3), the illumination time can be set according to the characteristics of the degradation process of the tetracycline organic pollutants, and can be set to 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours and the like.
The solution used in the detection method is that tetracycline organic pollutants are directly dissolved in pure deuterium water, then photocatalytic degradation is carried out, and the degradation process is detected in situ by an in-situ liquid nuclear magnetic technology; by the method, the conditions of the reduction of the concentration of the tetracycline organic pollutants and the degradation products can be rapidly and quantitatively detected.
The invention also provides application of the method in rapid quantitative detection of tetracycline organic pollutant concentration reduction.
The invention utilizes an in-situ high-field nuclear magnetic resonance technology which is completely different from a low-field nuclear magnetic resonance technology for detecting the reaction process based on magnetic resonance relaxation measurement in the detection principle.
The height of the light source from the liquid level in all tests of the invention must be kept consistent, and the height can be adjusted according to requirements. The distance between the light sources is 3 cm.
In one embodiment, the method of the present invention specifically comprises the steps of:
step 1: installation of equipment
And connecting the designed optical fiber bundle consisting of the bare fibers without metal wrapping with a light source through a condenser.
Step 2: sample loading
A test sample of aqueous tetracycline deuterium solution was added to a nuclear magnetic tube 5mm in diameter and 100mm in height. The nmr tube is then placed into the nmr apparatus.
And step 3: the optical fiber is led into the nuclear magnetic tube
And the other end of the optical fiber is led into a nuclear magnetic tube placed in nuclear magnetism, and the optical fiber is a bare optical fiber bundle. The rest of the wrapped optical fibers (non-bare optical fibers) and the light source device are placed outside the nuclear magnetic instrument.
In the invention, the optical fiber bundles introduced into the nuclear magnetic tube are all exposed; the whole optical fiber bundle outside the nuclear magnetic tube is wrapped by the protective layer.
And 4, step 4: pre-illumination signal acquisition
The primary data collection was performed every 5min on samples placed in the nuclear magnetic instrument before the light was turned on.
And 5: signal acquisition in illumination
And turning on a xenon lamp light source, and performing data acquisition on a sample placed in the nuclear magnetic instrument at specific time intervals, such as 30 min.
Step 6: analysis of results
Integrating the data obtained in the step 4 and the step 5 to obtain the molecular structures of the tetracycline organic pollutants respectively1Chemical structure content of H. The results were analyzed by mapping software and the final results were compared to standard uv spectrophotometry.
The design principle of the invention is that the molecular structure of the tetracycline organic pollutant is measured according to the photocatalytic degradation of the tetracycline organic pollutant and the nuclear magnetic resonance1H structure content is used for quantifying degradation results of tetracycline organic pollutants, and the tetracycline organic pollutants are established1The relationship between the content of H structure and the degradation process, contains1The different structures of H represent different degradation products, and the process of photocatalytic degradation of organic pollutants is finally researched through nuclear magnetism. On the basis, the photocatalytic process can be monitored in real time under the condition of no need of product separation by virtue of in-situ light source equipment. According to the invention, the in-situ illumination device can be built only by connecting the optical fiber with the xenon lamp light source through the condenser lens. In the invention, in-situ photocatalysis can be realized only by introducing the optical fiber into the nuclear magnetic tube filled with the mixture to be subjected to photocatalytic reaction; in the illumination process, the photocatalytic process can be monitored in real time by testing the atom content; therefore, the equipment provided by the invention is simple and convenient to build, simple in operation steps and novel in technical means. Compared with the traditional ultraviolet spectrophotometry, the method has the advantages that the obtained result is more accurate, the colorless group can be detected, and the technical means is simpler.
Compared with the prior art, the invention has the beneficial effects that:
(1) and the normal ex-situ1The H nuclear magnetic resonance spectrums are different, the technology can realize in-situ rapid detection of the molecular structure change of the tetracycline organic pollutants and the content change of various new structures formed by the degradation reaction in the degradation reaction process, a test sample does not need to be subjected to product separation, the detection time is shorter than 2min, and the detection is much faster than other existing detection means.
(2) The technology of the invention can accurately detect the structure and the content of the colorless product in the reaction process. The conventional method for judging the degradation degree through the absorbance change (such as UV-vis) can only detect the degradation reaction with color change in the degradation process, and cannot detect colorless toxic organic substances in the degradation process. The technology of the invention makes up the defects of the traditional technology in the aspect of detecting colorless toxic organic matters.
(3) The technology of the invention has obvious difference from the low-field nuclear magnetic resonance method in the detection principle of the detection in the chemical reaction process. Traditional low-field nmr methods are typically directed to detecting relaxation of the product and do not allow the specific chemical structure of the substance in the sample to be obtained. The technology disclosed by the invention is based on a high-resolution high-field nuclear magnetic technology, realizes in-situ rapid detection of chemical molecular structure change in the degradation reaction process and content change of various new structures formed by the degradation reaction, and is not limited by whether the degradation reaction has color change or not, so that the technology can judge the degradation process and the degradation degree of the chemical molecules more comprehensively and accurately.
(4) The test method is quick and simple, only specific pulses are needed to be applied to the sample, the experiment parameters are adjusted, and the system to be tested is not damaged. The detection range is wider, the detection system comprises the original solution and the reaction product thereof in the system, the reaction process is detected from the atomic layer, the detection precision is higher, the structure absorbance is not dependent, and the detection system can be used for monitoring colorless organic pollutants.
(5) The in-situ light source device has the advantages of ingenious design, simple operation and low cost, can detect the degradation process of the photocatalytic organic pollutants in real time, and simultaneously evaluates the degradation performance.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a tetracycline solution in example 1 of the present invention;
FIG. 2 is a schematic view of the overall appearance of in situ NMR-monitored photocatalytic tetracycline degradation in an embodiment of the present invention;
FIG. 3 is a graph showing photocatalytic tetracycline degradation activity of the photocatalyst measured by UV spectrophotometry in example 2 of the present invention;
FIG. 4 is a graph showing the variation of the nuclear magnetic resonance detection value at three sites of photocatalytic tetracycline along with the oxygen vacancy of the catalyst in example 2 of the present invention;
FIG. 5 is a graph showing the change of nuclear magnetism detection values of Ha-site positions of titanium dioxide photocatalytic degradation tetracycline in different oxygen vacancy concentrations with illumination time in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1: rapid detection of each H-containing structure content in tetracycline molecular structure
Step 1: preparation of tetracycline solution
Dissolving 10mg tetracycline hydrochloride in 10ml deuterium water to prepare a tetracycline hydrochloride deuterium water solution: 1 mg/ml.
Step 2: nuclear magnetic resonance testing
And (3) adding 0.5ml of the tetracycline solution obtained in the step (1) into a nuclear magnetic tube, and testing the content of each H-containing structure in the tetracycline molecular structure by using a single pulse sequence.
The model and specific parameters of the nuclear magnetic instrument in the step 2 are as follows: and a nuclear magnetic analyzer (500M), wherein the magnetic field intensity is 11.74T, the proton resonance frequency is 500MHz, and the diameter of the probe coil is 50 mm. The sampling parameters are as follows: the sampling time (AQ) is 2.5s, and the accumulated sampling Number (NS) is 16.
FIG. 1 is a nuclear magnetic spectrum of a tetracycline solution. As can be seen from FIG. 1, the peak at 0ppm is the internal standard TMSP, with a content of 1.604. mu. mol. The peak at 7.55ppm is derived from CH of the benzene ring (referred to as Ha in the present examples), the peak at 1.81ppm is attributable to CH of TC (referred to as Hb in the present examples), and the peak at 3.06ppm is attributable to CH of TC (referred to as Hc in the present examples). The content of internal reference TMSP (0ppm) in the system according to the invention was 1.604. mu. mol. By comparing their peak intensities with Ha, Hb, and Hc, the three H contents of tetracycline can be calculated. Therefore, the atomic content of each point of the tetracycline can be rapidly detected through nuclear magnetism.
The method has the advantages of rapidness, real-time performance and no need of pretreatment, and can realize atom level detection.
FIG. 2 is a schematic view of the overall appearance of photocatalytic tetracycline degradation monitored by in-situ nuclear magnetic resonance, and the in-situ nuclear magnetic resonance measurement method for photocatalytic tetracycline degradation reaction designed by the invention comprises the following steps: firstly, adding a suspension containing catalyst powder and an organic pollutant solution into a nuclear magnetic tube, carrying out ultrasonic homogenization, then assembling in-situ light source equipment, putting the nuclear magnetic tube into a nuclear magnetic resonance spectrometer cavity, introducing light into the nuclear magnetic tube through an optical fiber, and exciting a sample by using a single pulse sequence1H signal, and carrying out in-situ detection on the change condition of each chemical structure content of the system organic pollutant (tetracycline) along with the illumination time; and integrating the nuclear magnetic signal data obtained by the in-situ detection of different illumination time in the steps to finally obtain the degradation efficiency of the cyclic organic pollutants. The device can realize real-time monitoring of the degradation process of the tetracycline in the photocatalytic tetracycline heterogeneous degradation reaction process under the reaction condition.
Example 2: photocatalytic tetracycline degradation for detecting oxygen vacancy titanium dioxide in real time by in-situ nuclear magnetic resonance
Step one, preparation of catalyst
Preparing the titanium dioxide with oxygen vacancy by adopting the prior art: 0.1g of titanium dioxide was mixed with sodium borohydride, and the mixture was then thoroughly ground. The temperature was heated to 300 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere and held at that temperature for a certain period of time. The sample was then cooled to room temperature and washed several times with deionized water to remove residual sodium borohydride. After filtration, the filter cake was dried in an oven at 70 ℃ for 12 hours. The sample obtained is designated as n-TiO2Wherein "n" describes the amount of sodium borohydride added (n ═ 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, and 60 wt%), and is labeled as 10-TiO2，20-TiO2，30-TiO2，40-TiO2，50-TiO2，60-TiO2. Preparation of pure TiO by the same method2And does not contain sodium borohydride.
Step two, ultraviolet spectrophotometry performance characterization test
Uniformly dispersing 1mg of catalyst in 10ml of tetracycline solution with the concentration of 20mg/L at room temperature, and magnetically stirring the mixed solution for 0.5h in the dark to ensure that the catalyst and pollutants reach adsorption-desorption balance. The dark treated solution was placed under a 300W xenon lamp for photocatalytic experiments. During the irradiation, 3mL of the reaction solution was taken out of the reaction cell at a given time, filtered through a 0.22 μm Teflon filter, and the concentration of tetracycline was measured at a maximum absorption wavelength of 356nm using an ultraviolet-visible spectrophotometer. Fig. 3 is the photocatalytic tetracycline degradation activity of the photocatalyst measured using ultraviolet spectrophotometry. As can be seen from FIG. 3, the maximum absorption wavelength after light irradiation is blue-shifted from 356nm to 330nm as the concentration of oxygen vacancies in titanium dioxide increases, and therefore the tetracycline concentration measured by UV spectrophotometry is not sufficiently accurate.
Step three, in-situ nuclear magnetic resonance test
Adding 1mg of catalyst and 0.5ml of tetracycline solution of 1000mg/L into a nuclear magnetic tube, placing the nuclear magnetic tube into a nuclear magnetic cavity, connecting one end of an optical fiber to a xenon lamp light source, and introducing the other end of the optical fiber into nuclear magnetic to prepare for testing acquisition signals.
The samples in the nuclear magnetic tube were tested every 30min in the dark. And then, turning on a xenon lamp light source, and testing the sample in the nuclear magnetic tube every 30min in the illumination process.
The model and specific parameters of the nuclear magnetic instrument in the step 3 are as follows: and a nuclear magnetic analyzer (500M), wherein the magnetic field intensity is 11.74T, the proton resonance frequency is 500MHz, and the diameter of the probe coil is 50 mm. Selecting a ZG sequence, wherein the sampling parameters are as follows: the sampling time (AQ) is 2.5s, and the accumulated sampling Number (NS) is 16.
FIG. 4 is a graph of nuclear magnetic detection values of three points of photocatalytic tetracycline as a function of oxygen vacancies in the catalyst. Under the illumination condition, the degradation rates of the three points increase firstly and then decrease along with the increase of the oxygen vacancy concentration. The degradation degree is ranked as 30-TiO at 10min of illumination time2＞40-TiO2＞20-TiO2≈50-TiO2＞60-TiO2＞10-TiO2＞TiO2. The three point positions are analyzed one by one, and the Hb performance trend is consistent with that measured by the ultraviolet spectrophotometry shown in the figure 3. Therefore, Hb represents a color development group of tetracycline, Ha and Hc parts cannot be detected by ultraviolet spectrophotometry, Ha represents a benzene ring part which is a main environmental pollutant, and therefore, the degradation trend of the tetracycline is necessary to be detected at multiple points by a nuclear magnetic resonance technology.
FIG. 5 is a graph showing the change of nuclear magnetism detection values of Ha-site positions of titanium dioxide photocatalytic degradation tetracycline with different oxygen vacancy concentrations along with illumination time. Ordinate C/C0The ratio of the concentration of tetracycline in the solution after the reaction to that before the reaction is indicated. The degree of degradation is ranked 30-TiO2＞40-TiO2＞20-TiO2≈50-TiO2＞60-TiO2＞10-TiO2＞TiO2. It is feasible to evaluate the photocatalytic tetracycline degradation activity of the catalyst by detecting the change trend of tetracycline along with the illumination time by nuclear magnetic resonance.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, which is set forth in the following claims.
Claims (8)
1. The method for detecting the degradation of the tetracycline organic pollutant wastewater based on the in-situ high-field nuclear magnetic resonance technology is characterized in that the tetracycline organic pollutant is directly dissolved in pure deuterium water, and a single pulse sequence is used for exciting the tetracycline organic pollutant in the illumination condition1H signal, in-situ real-time monitoring chemical structure change of the tetracycline organic pollutants caused by photocatalytic degradation, and performing integral processing on content signal data in a spectrogram to quickly detect the conditions of concentration reduction and degradation products of the tetracycline organic pollutants so as to represent the real degradation process and efficiency of the tetracycline organic pollutants, wherein the specific process of the method comprises the following steps:
step (1): adding the suspension containing the catalyst powder and the tetracycline organic pollutant solution into a matched nuclear magnetic tube, and performing ultrasonic homogenization;
step (2): assembling in-situ light source equipment, putting the nuclear magnetic tube filled with the sample to be detected into a cavity of a liquid high-field nuclear magnetic resonance spectrometer, and introducing light into the nuclear magnetic tube through an optical fiber;
and (3): excitation of tetracycline organic contaminants using a single pulse train1H signal to various sites of tetracycline organic contaminants1H signal changes with illumination time and is detected in situ;
and (4): in-situ detecting each site obtained in the step (3) at different illumination time1And (4) performing integration processing on the H signal data to finally obtain the degradation efficiency of the tetracycline organic pollutants.
2. The method of claim 1, wherein the high field is a magnetic field strength greater than 200M; the whole in situ test process does not need product separation.
3. The method of claim 1, wherein in step (1), the catalyst is TiO2、10-TiO2、20-TiO2、30-TiO2、40-TiO2、50-TiO2、60-TiO2One or more of the above; the adding amount of the catalyst powder is 0.5 mg-10 mg; the organic contaminants comprise one or more of tetracycline organic contaminants; the volume of the added tetracycline organic pollutant solution is 1 mL-2 mL, and the concentration is 1 mg/L-2000 mg/L; the ultrasonic power is 40W; the ultrasonic temperature is 25 ℃; the ultrasonic treatment time is 5 min; the ultrasonic frequency was 70 kHz.
4. The method of claim 1, wherein in step (1), the nuclear magnetic tube has a diameter of 5mm and a height of 100 mm.
5. The method of claim 1, wherein in step (2), the in-situ light source device comprises a light source and an optical fiber, and the light source and the nuclear magnetic tube are connected by the optical fiber.
6. The method of claim 5, wherein the optical fiber is a custom metal free wrapped fiber bundle; the optical fiber bundle consists of 5-7 optical fibers, and the diameter of the optical fiber bundle is 0.2-0.3 cm; the light source is one or more of a common xenon lamp light source, a mercury lamp light source and a metal halide lamp light source.
7. The method according to claim 1, wherein in the step (3), the light irradiation time is set according to the characteristics of the degradation process of the experimental tetracycline organic pollutants and is 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours and 3 hours.
8. Use of the method according to any one of claims 1 to 7 for quantitative determination of the concentration of tetracycline organic pollutants and the composition and content of degradation products.
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