CN115950864A - Water pollution tracing detection method based on three-dimensional fluorescence spectrometry - Google Patents
Water pollution tracing detection method based on three-dimensional fluorescence spectrometry Download PDFInfo
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Abstract
The invention relates to the field of sewage tracing detection, in particular to a water pollution tracing detection method based on a three-dimensional fluorescence spectrometry, which comprises the following steps of obtaining a polluted water sample in a water quality detection area; pretreating a fluorescence area of a polluted water sample; generalizing substance molecules in the polluted water sample into an energy level model, analyzing a three-dimensional fluorescence map, and finally determining the relation between two characteristic parameters in the polluted water sample; establishing a water area space distribution model, and establishing a source tracing detection semantic network; and matching the collected data of the polluted water sample with the water area space distribution model to complete the tracing operation. The method realizes the tracing of pollutants by using the three-dimensional fluorescence spectrometry, has short time, high accuracy and reliable result in the whole process, and solves the problems of long period, secondary pollution easily caused by improper treatment of medicines and the like in the tracing process of the traditional method; a water area space distribution model is established, and convenience is provided for tracing the source of pollutants.
Description
Technical Field
The invention relates to the field of sewage tracing detection, in particular to a water pollution tracing detection method based on a three-dimensional fluorescence spectrometry.
Background
The water quality safety is closely related to the national civilization, along with the rapid promotion of industrialization and the rapid development of national economy, water pollution events caused by environmental problems are frequent, enterprises steal and drain water, huge damage is caused to the water environment, and the problems of weak monitoring, slow pollution source searching and the like existing in water quality monitoring in China are reflected.
At present, the water quality monitoring technology in China mainly takes a physicochemical monitoring technology as a main part, although the traditional national standard methods have high reliability and good reproducibility of detection results, the method has many defects in practical application, and can cause secondary pollution to the environment if the medicines are not treated properly, and the general detection period of the traditional chemical methods is very long, so that results cannot be obtained in time, and pollution sources are difficult to trace in time, thereby causing continuous pollution and being difficult to treat efficiently.
The three-dimensional fluorescence spectrum detection method has the characteristics of high sensitivity, good selectivity, quick response, low detection limit and the like. The fluorescence peak is taken as a typical index of the three-dimensional fluorescence recognition pollutant, the positions and the number of the fluorescence peaks of different pollutants are different, and the source of the pollutant can be judged by comparing the overall similarity when the similarity is more than 90%.
Therefore, the technical problem to be solved by the technical staff in the art is to design a water pollution tracing detection method based on three-dimensional fluorescence spectroscopy to overcome the problems that the traditional pollution tracing method needs long time and detection results are easy to be wrong due to observation errors.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a water pollution tracing detection method based on a three-dimensional fluorescence spectrometry.
The invention is realized by the following technical scheme: a water pollution tracing detection method based on three-dimensional fluorescence spectrometry comprises the following steps:
s1: acquiring a polluted water sample in a water quality detection area;
s2: preprocessing the fluorescence area of the polluted water sample in the step S1;
s3: generalizing substance molecules in the polluted water sample into an energy level model, analyzing a three-dimensional fluorescence spectrum, and finally determining the relation between two characteristic parameters in the polluted water sample;
s4: on the basis of the step S3, establishing a water area space distribution model and establishing a source tracing detection semantic network;
s5: and on the basis of the step S4, matching the collected data of the polluted water sample with the water area space distribution model to finish the tracing operation.
According to the above technical solution, preferably, the number and the longitude and latitude value of the contaminated water sample obtained in step S1 are recorded.
According to the above technical solution, preferably, the preprocessing in S2 specifically includes:
preprocessing a three-dimensional fluorescence area: carrying out inner filtering effect correction on the fluorescence area;
and (3) Rayleigh scattering pretreatment: subtracting the fluorescence spectrum of the polluted water sample from the fluorescence spectrum of the ionized water, and setting the fluorescence data at the excitation wavelength equal to the emission wavelength as 0 or as a non-numerical value;
performing Raman scattering pretreatment: the fluorescence data of the contaminated water sample was subtracted from the fluorescence spectrum of the water.
According to the above technical solution, preferably, S3 specifically includes:
through the process of radiation transition of fluorescent molecules from a high-energy excitation state to a low-energy excitation state in the form of release radiation, substance molecules in the polluted water sample are generalized into an energy level model, and the expansion rate is as follows:
wherein M is a molecular spontaneous parameter; m 1 Is the fluorescent ion density; s 1 Is the molecular excitation rate; omega is the excitation rate;
analyzing the three-dimensional fluorescence spectrum by adopting a parallel factor method, and establishing a data model by using two continuous characteristic parameters in the polluted water sample, wherein the equation of the data model can be expressed as follows:
wherein x is f Is a fitting function; a is f Is a characterization function; epsilon is the laser mass emission spectrum; f is a fluorophore emission spectrum;
the relationship between the two characteristic parameters in the contaminated water sample can now be expressed as follows:
wherein, X 1 ,X 2 Corresponding characteristic parameters in the water sample; e (X) 1 )、E(X 2 ) Are respectively a characteristic parameter X 1 ,X 2 Is measured.
According to the above technical solution, preferably, S4 specifically includes: calculating the rate value when the linear balance is kept according to the two characteristic parameters obtained in the step S3, taking the rate value as a judgment condition of the polluted isotope, converting the detected polluted water sample data into a corresponding linear function, and converting the data into a linear function by the isotope 14 C, judging the pollution time of the water quality detection area, transforming the element numerical values into corresponding orthogonal matrix element numerical values by using a tensor decomposition method-Tucker 3, selecting one of the main components as a processing fraction, thereby solving the residual error problem of the elements, and calculating to obtain the pollution element approximate value of the polluted water sample after solving the residual error problem of the elements, wherein the calculation method can be represented by the following formula:
wherein A is k An approximation function for the element; d (c) i ) As a function of the concentration of the element; x k Is an orthogonal function;
decomposing parameters between pollution time and pollution elements, and calculating according to the following formula:
wherein c is a contamination parameter; i. j is an element estimation factor; t is t i 、t j Is a factor deviation;
and (4) taking the calculated result as a control condition, and after a spatial distribution model is obtained, establishing a traceability detection semantic network to form a pollution traceability detection process.
According to the above technical solution, preferably, S5 specifically includes: integrating the polluted water sample data in a multi-source heterogeneous form, establishing an entity relation of pollution elements in the polluted water sample by using an extraction method, and completing construction of a knowledge map; utilizing the Lambert beer law and the efficiency of the knowledge graph generation to further obtain the conversion rate of the knowledge base, wherein the calculation formula is as follows;
wherein C is the water area coverage of the map;
the points are tracing standard comparison points; e.g. of the type i Is a knowledge base functional relationship;
carrying out iterative processing on the knowledge base, wherein the calculation formula is as follows:
wherein, W k 、W x Different states in the iterative process; lambda is a demixing parameter;
and continuously processing the polluted water sample data in the iterative process so as to complete the matching of the polluted water sample data and the water area space distribution model.
According to the above technical solution, preferably, in order to reduce the observation error in the tracing process, a condition index is introduced, and a calculation formula thereof is as follows:
wherein, R is a condition index, exp (E) is an observation function, namely a parameter of the source tracing point.
According to the technical scheme, preferably, when the numerical value of the condition index is 0.5, the tracing process is good, the result is reliable, and the tracing is completed.
The invention has the beneficial effects that: the method realizes the tracing of pollutants by using the three-dimensional fluorescence spectrometry, has short time, high accuracy and reliable result in the whole process, and solves the problems of long period, secondary pollution easily caused by improper treatment of medicines and the like in the tracing process of the traditional method; introducing a condition index to reduce observation errors possibly generated in the tracing process and improve the accuracy of the tracing result; a water area spatial distribution model is established, and convenience is provided for tracing the source of pollutants.
Drawings
Fig. 1 shows a flow chart of the method of the invention.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
As shown in the figure, the invention provides a water pollution tracing detection method based on three-dimensional fluorescence spectrometry, which comprises the following steps:
s1: acquiring a polluted water sample in a water quality detection area;
s2: preprocessing the fluorescence area of the polluted water sample in the step S1;
s3: generalizing substance molecules in the polluted water sample into an energy level model, analyzing a three-dimensional fluorescence spectrum, and finally determining the relation of two characteristic parameters in the polluted water sample by using a three-dimensional fluorescence spectrum method;
s4: on the basis of the step S3, establishing a water area space distribution model and establishing a tracing detection semantic network;
s5: and on the basis of the step S4, matching the collected data of the polluted water sample with the water area space distribution model to finish the tracing operation.
According to the above embodiment, it is preferable that the number and the latitude and longitude values are recorded for the contaminated water sample acquired in step S1.
According to the above embodiment, preferably, the preprocessing in S2 specifically includes:
preprocessing a three-dimensional fluorescence area: carrying out inner filtering effect correction on the fluorescence area;
and (3) Rayleigh scattering pretreatment: subtracting the fluorescence spectrum of the polluted water sample from the fluorescence spectrum of the ionized water, and setting the fluorescence data at the excitation wavelength equal to the emission wavelength as 0 or as a non-numerical value;
performing Raman scattering pretreatment: the fluorescence data of the contaminated water sample was subtracted from the fluorescence spectrum of the water.
According to the above embodiment, preferably, S3 specifically includes:
through the process of radiation transition of fluorescent molecules from a high-energy excitation state to a low-energy excitation state in the form of release radiation, substance molecules in the polluted water sample are generalized into an energy level model, and the expansion rate is as follows:
wherein M is a molecular spontaneous parameter; m 1 Is the fluorescent ion density; s 1 Is the molecular excitation rate; omega is the excitation rate;
analyzing the three-dimensional fluorescence spectrum by adopting a parallel factor method, and establishing a data model by using two continuous characteristic parameters in the polluted water sample, wherein the equation of the data model can be expressed as follows:
wherein x is f Is a fitting function; a is f Is a characterization function; epsilon is the laser mass emission spectrum; f is a fluorophore emission spectrum；
The relationship between the two characteristic parameters in the contaminated water sample can now be expressed as follows:
wherein X 1 ,X 2 Corresponding characteristic parameters in the water sample; e (X) 1 )、E(X 2 ) Are respectively a characteristic parameter X 1 ,X 2 Is measured.
According to the above embodiment, preferably, S4 specifically includes: calculating the rate value when the linear balance is kept according to the two characteristic parameters obtained in the step S3, taking the rate value as a judgment condition of the polluted isotope, converting the detected polluted water sample data into a corresponding linear function, and converting the data into a linear function by the isotope 14 C, judging the pollution time of the water quality detection area, transforming the element numerical values into corresponding orthogonal matrix element numerical values by using a tensor decomposition method-Tucker 3, selecting one of the main components as a processing fraction, thereby solving the residual error problem of the elements, and calculating to obtain the pollution element approximate value of the polluted water sample after solving the residual error problem of the elements, wherein the calculation method can be represented by the following formula:
wherein A is k An approximation function for the element; d (c) i ) As a function of the concentration of the element; x k Is an orthogonal function;
decomposing parameters between pollution time and pollution elements, and calculating according to the following formula:
wherein c is a contamination parameter; i. j is an element estimation factor; t is t i 、t j Is a factor deviation;
and (4) taking the calculated result as a control condition, and after a spatial distribution model is obtained, establishing a traceability detection semantic network to form a pollution traceability detection process.
According to the above embodiment, preferably, S5 specifically includes: integrating and processing the polluted water sample data in a multi-source heterogeneous form, and establishing an entity relationship of the pollution elements in the polluted water sample by using an extraction method to complete the construction of a knowledge map; obtaining the conversion rate of the knowledge base by utilizing the Lambert beer law and the efficiency of the generation of the knowledge graph, wherein the calculation formula is as follows;
wherein, C is the water area coverage of map coverage;
the points are tracing standard comparison points; e.g. of the type i Is a knowledge base functional relationship;
carrying out iterative processing on the knowledge base, wherein the calculation formula is as follows:
wherein, W k 、W x Different states in the iterative process; lambda is a demixing parameter;
and continuously processing the polluted water sample data in the iterative process so as to complete the matching of the polluted water sample data and the water area space distribution model.
According to the above embodiment, preferably, in order to reduce the observation error in the tracing process, a condition index is introduced, and the calculation formula is as follows:
where R is a condition index and exp (E) is an observation function, i.e., a parameter of the traceable landmark. When the numerical value of the condition index is 0.5, the tracing process is good, the result is reliable, and the tracing is completed.
The following table is a comparison graph of the accuracy of the invention and the traditional tracing method:
it can be seen that the accuracy of the tracing detection method of the invention is much higher than that of the traditional tracing method.
The invention has the beneficial effects that: the method has the advantages that the three-dimensional fluorescence spectrometry is utilized to trace the source of pollutants, the whole process is short in time, high in accuracy and reliable in result, and the problems that the period is long, secondary pollution is easily caused due to improper treatment of medicines and the like in the tracing process of the traditional method are solved; introducing a condition index to reduce observation errors possibly generated in the tracing process and improve the accuracy of the tracing result; a water area spatial distribution model is established, and convenience is provided for tracing the source of pollutants.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A water pollution tracing detection method based on three-dimensional fluorescence spectrometry is characterized by comprising the following steps:
s1: acquiring a polluted water sample in a water quality detection area;
s2: preprocessing the fluorescence area of the polluted water sample in the step S1;
s3: generalizing substance molecules in the polluted water sample into an energy level model, analyzing a three-dimensional fluorescence map, and finally determining the relation between two characteristic parameters in the polluted water sample;
s4: on the basis of the step S3, establishing a water area space distribution model and establishing a tracing detection semantic network;
s5: and on the basis of the step S4, matching the collected data of the polluted water sample with the water area space distribution model to finish the tracing operation.
2. The water pollution traceability detection method based on three-dimensional fluorescence spectrometry as claimed in claim 1, wherein the number and the longitude and latitude values of the polluted water sample obtained in step S1 are recorded.
3. The method for detecting the water pollution source tracing based on the three-dimensional fluorescence spectrometry according to claim 1, wherein the preprocessing in S2 specifically comprises:
preprocessing a three-dimensional fluorescence area: carrying out inner filtering effect correction on the fluorescence area;
and (3) performing Rayleigh scattering pretreatment: subtracting the fluorescence spectrum of the polluted water sample from the fluorescence spectrum of the ionized water, and setting the fluorescence data at the excitation wavelength equal to the emission wavelength as 0 or as a non-numerical value;
performing Raman scattering pretreatment: the fluorescence data of the contaminated water sample was subtracted from the fluorescence spectrum of the water.
4. The method for detecting water pollution tracing based on three-dimensional fluorescence spectrometry as claimed in claim 1, wherein said S3 specifically comprises:
through the process of radiation transition of fluorescent molecules from a high-energy excitation state to a low-energy excitation state in the form of release radiation, substance molecules in the polluted water sample are generalized into an energy level model, and the expansion rate is as follows:
wherein M is a molecular spontaneous parameter; m 1 Is the fluorescent ion density; s 1 Is the molecular excitation rate; omega is the excitation rate;
analyzing the three-dimensional fluorescence spectrum by adopting a parallel factor method, and establishing a data model by using two continuous characteristic parameters in the polluted water sample, wherein the equation of the data model can be expressed as follows:
wherein x is f Is a fitting function; a is f Is a characterization function; epsilon is the laser mass emission spectrum; f is a fluorophore emission spectrum;
the relationship between the two characteristic parameters in the contaminated water sample can now be expressed as follows:
wherein, X 1 ,X 2 Corresponding characteristic parameters in the water sample; e (X) 1 )、E(X 2 ) Are respectively a characteristic parameter X 1 ,X 2 Is measured.
5. The method for detecting water pollution source tracing based on three-dimensional fluorescence spectrometry as claimed in claim 1, wherein said S4 specifically comprises: calculating the rate value when the linear balance is kept according to the two characteristic parameters obtained in the step S3, taking the rate value as a judgment condition of the polluted isotope, converting the detected polluted water sample data into a corresponding linear function, and converting the data into a linear function by the isotope 14 C, judging the pollution time of the water quality detection area, transforming the element values into corresponding orthogonal matrix element values by using a tensor decomposition method-Tucker 3, selecting one of the main components as a processing fraction, thereby solving the residual error problem of the elements, and calculating to obtain the pollution element approximate value of the polluted water sample after solving the residual error problem of the elements, wherein the calculation method can be represented by the following formula:
wherein A is k An approximation function for the element; d (c) i ) As a function of the concentration of the element; x k Is an orthogonal function;
decomposing parameters between pollution time and pollution elements, and calculating according to the following formula:
wherein c is a contamination parameter; i. j is an element estimation factor; t is t i 、t j Is a factor deviation;
and (4) taking the calculated result as a control condition, and after a spatial distribution model is obtained, establishing a traceability detection semantic network to form a pollution traceability detection process.
6. The method for detecting water pollution source tracing based on three-dimensional fluorescence spectrometry as claimed in claim 1, wherein said S5 specifically comprises: integrating the polluted water sample data in a multi-source heterogeneous form, establishing an entity relation of pollution elements in the polluted water sample by using an extraction method, and completing construction of a knowledge map; obtaining the conversion rate of the knowledge base by utilizing the Lambert beer law and the efficiency of the generation of the knowledge graph, wherein the calculation formula is as follows;
wherein, C is the water area coverage of map coverage;
the points are tracing standard comparison points; e.g. of the type i Is a knowledge base functional relationship;
carrying out iterative processing on the knowledge base, wherein the calculation formula is as follows:
wherein, W k 、W x Different states in the iterative process; lambda is a demixing parameter；
And continuously processing the polluted water sample data in the iterative process so as to complete the matching of the polluted water sample data and the water area space distribution model.
7. The method for detecting water pollution tracing based on three-dimensional fluorescence spectrometry as claimed in claim 1, wherein in order to reduce the observation error in the tracing process, a condition index is introduced, and the calculation formula is as follows:
where R is a condition index and exp (E) is an observation function, i.e., a parameter of the traceable landmark.
8. The water pollution traceability detection method based on three-dimensional fluorescence spectrometry as claimed in claim 7, wherein when the value of the condition index is 0.5, the traceability process is good, the result is reliable, and the traceability is completed.
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