Water quality detection concentration calculation method and system
By applying hidden transfer matrix technology on microfluidic chips, the problem of concentration calculation distortion in multi-index water quality detection is solved, and the high accuracy of total nitrogen and COD concentration detection is achieved.
Patent Information
- Application Number
- CN202411371698.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-29
- Publication Date
- 2025-02-25
- Estimated Expiration
- 2044-09-29
AI Technical Summary
When multi-index water quality is detected on a microfluidic chip, the contact time between chemical reagents and chip materials is extended, resulting in photoelectric detection distortion between COD and total nitrogen, which in turn affects the accuracy of concentration calculation.
The hidden transfer matrix technology is used to estimate the real total nitrogen and COD concentration of the water sample through multiple photoelectric detection values, which improves the accuracy of the detection results.
It effectively solves the problem of concentration calculation distortion during multi-index detection, improves the accuracy of total nitrogen and COD concentration detection, and makes the detection results consistent with the independent chip detection results.
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Figure CN119510330A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of water quality concentration detection, and in particular to a water quality detection concentration calculation method and system. Background Art
[0002] After the injection molding, bonding, hot pressing and other processes, the microfluidic chip has formed a chip body with a sealed inner cavity. If the water quality concentration test of each indicator is only for an independent microfluidic chip, it can fully meet the requirements of different indicators. For example, for the total nitrogen indicator, as long as the cleanliness of the quartz surface can be guaranteed; for the COD indicator, as long as the water sample can be quickly transferred to the detection cavity for photoelectric detection after digestion, the reaction degree of the reagent with the microfluidic chip material in a short time is extremely low; relatively speaking, the chemical reagents of ammonia nitrogen and total phosphorus are the least sensitive to the microfluidic chip material. As long as the inner cavity is clean and free of impurities, the change of water sample deterioration is very stable. However, once the microfluidic chip is tested, its internal chemical molecules are changed, and it cannot be cleaned and retested like traditional experimental equipment.
[0003] In order to improve the efficiency of microfluidic chips, it is very important to integrate multiple different indicators on one chip. However, the integrated detection of four indicators will prolong the contact time between chemical reagents and microfluidic chip materials, which will cause distortion of photoelectric detection of COD and total nitrogen after all four indicators have completed the transfer and color development. The distortion of the photoelectric detection signal value will cause the distortion of the calculated concentration value. How to make the detection process of different indicators compatible and make the detection concentration the same as that of four independent microfluidic chips is a technical problem that needs to be solved in multi-indicator microfluidic water quality detection. However, there is currently no technical solution that can solve the above technical problems, and there is no method and system for calculating water quality detection concentration based on microfluidic chips. Summary of the invention
[0004] The present invention provides a method and system for calculating water quality detection concentration. After the single-index detection is converted and integrated into the multi-index detection, the accuracy of the total nitrogen and COD detection results is improved by using implicit transfer matrix to address the impact of compatibility issues of different indicator processes on the accuracy of total nitrogen and COD detection results.
[0005] In a first aspect, the present invention provides a method for calculating water quality detection concentration, comprising:
[0006] For the target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, the target water sample is continuously subjected to photoelectric detection for a preset number of times to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration for the preset number of times, wherein different wavelengths correspond to photoelectric detection of different water quality indicators;
[0007] Determine the actual total phosphorus concentration of the target water sample according to the concentration average of the total phosphorus concentrations of the preset times, and determine the actual ammonia nitrogen concentration of the target water sample according to the concentration average of the ammonia nitrogen concentrations of the preset times;
[0008] An initial total nitrogen concentration matrix is constructed according to the total nitrogen concentrations of a preset number of times, an actual total nitrogen concentration matrix is calculated according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and the actual total nitrogen concentration of the target water sample is determined according to the maximum value in the actual total nitrogen concentration matrix; an initial COD concentration matrix is constructed according to the COD concentrations of a preset number of times, an actual COD concentration matrix is calculated according to the initial COD concentration matrix and the COD implicit transfer matrix, and the actual COD concentration of the target water sample is determined according to the maximum value in the actual COD concentration matrix;
[0009] The total nitrogen hidden transfer matrix is determined by performing photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample total nitrogen concentration matrix constructed by the total nitrogen concentrations of the samples at different concentrations for a preset number of times, and calculating based on the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations;
[0010] The COD latent transfer matrix is obtained by performing photoelectric detection on sample water quality at different concentrations for a preset number of times, and obtaining a sample COD concentration matrix constructed by the sample COD concentrations at different concentrations for a preset number of times, which is determined after calculation based on the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
[0011] According to the water quality detection concentration calculation method provided by the present invention, before calculating the actual total nitrogen concentration matrix according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, the total nitrogen implicit transfer matrix is determined after calculation according to the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations:
[0012]
[0013] in, is the total nitrogen implicit transfer matrix, P T is the transpose of P, P is the total nitrogen concentration matrix of the samples, and Q is the total nitrogen standard solution matrix at different concentrations.
[0014] According to the water quality detection concentration calculation method provided by the present invention, the sample total nitrogen concentration matrix P is:
[0015]
[0016] The total nitrogen standard solution matrix Q at different concentrations is:
[0017]
[0018] The total nitrogen implicit transfer matrix for:
[0019]
[0020] M is the preset number, and Z is the number of different concentrations.
[0021] According to the water quality detection concentration calculation method provided by the present invention, before calculating the actual COD concentration matrix according to the initial COD concentration matrix and the COD implicit transfer matrix, the COD implicit transfer matrix is determined after calculation according to the sample COD concentration matrix and the COD standard solution matrix at different concentrations:
[0022]
[0023] degree matrix, H is the COD standard solution matrix at different concentrations.
[0024] According to the water quality detection concentration calculation method provided by the present invention, the sample COD concentration matrix C is:
[0025]
[0026] The COD standard solution matrix H at different concentrations is:
[0027]
[0028] The COD implicit transfer matrix ω is:
[0029]
[0030] M is the preset number, and Z is the number of different concentrations.
[0031] According to the water quality detection concentration calculation method provided by the present invention, after determining the actual COD concentration of the target water sample according to the maximum value in the actual COD concentration matrix, the method further includes:
[0032] Calculate the target total phosphorus concentration variance based on the total phosphorus concentration of the preset times, and calculate the target ammonia nitrogen concentration variance based on the ammonia nitrogen concentration of the preset times;
[0033] When the target total phosphorus concentration variance is within the preset total phosphorus concentration variance interval, and the target ammonia nitrogen concentration variance is within the preset ammonia nitrogen concentration variance interval, the actual total nitrogen concentration and the actual COD concentration of the target water sample are determined to be valid calculation results; otherwise, the actual total nitrogen concentration and the actual COD concentration of the target water sample are determined to be invalid calculation results.
[0034] According to the water quality detection concentration calculation method provided by the present invention, before calculating the target total phosphorus concentration variance according to the total phosphorus concentration of the preset number of times and calculating the target ammonia nitrogen concentration variance according to the ammonia nitrogen concentration of the preset number of times, the method further includes:
[0035] Performing photoelectric detection on the sample water quality for a preset number of times to obtain the total phosphorus concentration of the sample at different concentrations for a preset number of times, and performing photoelectric detection on the sample water quality for a preset number of times to obtain the ammonia nitrogen concentration of the sample at different concentrations for a preset number of times;
[0036] For each concentration, according to the total phosphorus concentrations of all samples at the concentration, the variance of the total phosphorus concentration of the sample is calculated, all concentrations are traversed, the variance of the total phosphorus concentration of the sample at each concentration is determined, and the preset total phosphorus concentration variance interval is determined according to the maximum and minimum variances of the total phosphorus concentration of the sample at all concentrations;
[0037] For each concentration, the variance of the sample ammonia nitrogen concentration is calculated based on the ammonia nitrogen concentrations of all samples at the concentration, all concentrations are traversed to determine the variance of the sample ammonia nitrogen concentration at each concentration, and the preset ammonia nitrogen concentration variance interval is determined based on the maximum and minimum values of the variance of the sample ammonia nitrogen concentrations at all concentrations.
[0038] According to the water quality detection concentration calculation method provided by the present invention, the water quality indicators include total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration, and the different wavelengths correspond to the photoelectric detection of different water quality indicators, including:
[0039] Photoelectric detection of total phosphorus corresponds to a wavelength of 700 nm;
[0040] Photoelectric detection of total nitrogen corresponds to a wavelength of 220 nm;
[0041] Photoelectric detection of COD corresponds to a wavelength of 440 nm;
[0042] The photoelectric detection of ammonia nitrogen corresponds to a wavelength of 700 nm.
[0043] According to the water quality detection concentration calculation method provided by the present invention, before constructing an initial total nitrogen concentration matrix according to the total nitrogen concentrations of a preset number of times, the method further includes:
[0044] Performing photoelectric detection for a preset number of times on the total nitrogen standard solution at different concentrations, each photoelectric detection time lasting for a preset time, and determining the concentration of the photoelectric signal corresponding to the photoelectric detection as the total nitrogen concentration, until the total nitrogen concentration of the preset number of times is obtained;
[0045] The different concentrations are different concentrations with uniform values.
[0046] In a second aspect, a water quality detection concentration calculation system is provided, wherein the water quality detection concentration calculation system is a microfluidic chip, and the microfluidic chip is used to:
[0047] For the target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, the target water sample is continuously subjected to photoelectric detection for a preset number of times to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration for the preset number of times, wherein different wavelengths correspond to photoelectric detection of different water quality indicators;
[0048] Determine the actual total phosphorus concentration of the target water sample according to the concentration average of the total phosphorus concentrations of the preset times, and determine the actual ammonia nitrogen concentration of the target water sample according to the concentration average of the ammonia nitrogen concentrations of the preset times;
[0049] An initial total nitrogen concentration matrix is constructed according to the total nitrogen concentrations of a preset number of times, an actual total nitrogen concentration matrix is calculated according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and the actual total nitrogen concentration of the target water sample is determined according to the maximum value in the actual total nitrogen concentration matrix; an initial COD concentration matrix is constructed according to the COD concentrations of a preset number of times, an actual COD concentration matrix is calculated according to the initial COD concentration matrix and the COD implicit transfer matrix, and the actual COD concentration of the target water sample is determined according to the maximum value in the actual COD concentration matrix;
[0050] The total nitrogen hidden transfer matrix is determined by performing photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample total nitrogen concentration matrix constructed by the total nitrogen concentrations of the samples at different concentrations for a preset number of times, and calculating based on the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations;
[0051] The COD latent transfer matrix is obtained by performing photoelectric detection on sample water quality at different concentrations for a preset number of times, and obtaining a sample COD concentration matrix constructed by the sample COD concentrations at different concentrations for a preset number of times, which is determined after calculation based on the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
[0052] In order to improve the utilization efficiency of the microfluidic chip, the present invention integrates the detection of multiple different indicators on one chip. When the microfluidic chip is used to detect the water quality concentration, in the process of synchronous centrifugal transfer of multiple indicators and mixing of pre-set reagents, different chemical reagents have different reaction sensitivities to the microfluidic chip material, resulting in abnormal distortion of the water quality detection concentration. In order to be compatible with the detection processes of different indicators and make the final detection concentration result as accurate as when four independent microfluidic chips are detected separately, the present invention proposes a calculation method for restoring the actual water quality concentration using an implicit transfer matrix, thereby improving the accuracy of the total nitrogen concentration and COD concentration detection results. Since the detection processes of total phosphorus and ammonia nitrogen include a color development process, extending the photoelectric detection time is to extend the color development process, which has no effect on the two indicators of ammonia nitrogen and total phosphorus.
[0053] The reason why the present invention can use the errors of ammonia nitrogen and total phosphorus to determine whether the actual total nitrogen concentration and the actual COD concentration of the target water sample are valid calculation results is because the present invention can solve the distortion problem when promoting from single-indicator detection to multi-indicator detection. If there are problems with the materials and processes of this microfluidic chip itself, the accurate calculation of water quality concentration cannot be achieved through the present invention. This is the boundary range within which the present invention can solve this problem. Ultimately, when the detection of multiple different indicators is integrated on the same chip, the detection results of total nitrogen concentration, COD concentration, total phosphorus concentration and ammonia nitrogen concentration are all very accurate, shortening the detection time and improving the detection efficiency. BRIEF DESCRIPTION OF THE DRAWINGS
[0054] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0055] Figure 1 It is a schematic diagram of the flow of the water quality detection concentration calculation method provided by the present invention;
[0056] Figure 2 This is one of the structural schematic diagrams of the water quality detection concentration calculation system provided by the present invention;
[0057] Figure 3 This is the second structural schematic diagram of the water quality detection concentration calculation system provided by the present invention;
[0058] Figure 4 It is a variation trend diagram of different standard liquid points provided by the present invention;
[0059] Figure 5 It is a structural schematic diagram of the electronic device provided by the present invention. DETAILED DESCRIPTION
[0060] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the drawings of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0061] Traditional chemical reagent water quality testing methods integrate the complex and cumbersome water quality testing procedures of digestion, titration, mixing, colorimetry, and calculation into micrometer-scale chips to automatically complete the entire analysis process. Microfluidic chips have the advantages of light size, small amount of samples and reagents, low energy consumption, fast reaction speed, large-scale parallel processing, and disposable. However, there are not many applications of microfluidic chips in analytical chemistry of indicators such as ammonia nitrogen, total phosphorus, total nitrogen, and COD in water quality testing. This is mainly restricted by the material properties and process bonding of microfluidic chips. Although there are many different types of materials such as silicon, metal, polymer, glass, quartz, etc. in material selection, there are not many materials that can meet the COD index, and the mold processing and bonding process of polymer or quartz is also an important link that affects whether the water quality test results are true and effective.
[0062] The entire manufacturing process of microfluidic chips is divided into several main steps, including injection molding, test piece bonding, pressure-sensitive film hot pressing, and pre-reagent assembly. It is different from the instruments used in traditional water quality testing, which can be cleaned and dried in advance according to national standards and stored in a clean environment for regular inspection, maintenance, and maintenance. If the single-indicator microfluidic chip detection is promoted to the simultaneous water quality concentration detection of four indicators, a lot of time can be saved, because there are many overlapping action processes in the execution of the four indicators, such as injection, transfer, and photoelectric detection, and the four indicators can more completely represent the water quality characteristics of a sampling point.
[0063] The present invention aims to design a method for water quality detection using a multi-index microfluidic chip. Figure 2 As shown, the detection carrier is based on a microfluidic chip, and the chip shape is a circular chip. Fan-shaped chips of four different water quality parameters, namely total phosphorus, total nitrogen, COD, and ammonia nitrogen, are distributed in the circular chip. The initial value is calculated by multiple photoelectric detection values of the four indicators and a preset model algorithm to estimate the true concentration value. The preset model algorithm includes the least squares method and fusion discrimination of different indicators.
[0064] Figure 1 : is a schematic flow chart of a method for calculating water quality detection concentration provided by the present invention, wherein the method for calculating water quality detection concentration comprises:
[0065] Step 101: for a target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, the target water sample is continuously subjected to photoelectric detection for a preset number of times to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration for the preset number of times, wherein different wavelengths correspond to photoelectric detection of different water quality indicators;
[0066] Step 102: determining the actual total phosphorus concentration of the target water sample according to the concentration mean of the total phosphorus concentration of a preset number of times, and determining the actual ammonia nitrogen concentration of the target water sample according to the concentration mean of the ammonia nitrogen concentration of a preset number of times;
[0067] Step 103, constructing an initial total nitrogen concentration matrix according to the total nitrogen concentrations of a preset number of times, calculating an actual total nitrogen concentration matrix according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and determining the actual total nitrogen concentration of the target water sample according to the maximum value in the actual total nitrogen concentration matrix; constructing an initial COD concentration matrix according to the COD concentrations of a preset number of times, calculating an actual COD concentration matrix according to the initial COD concentration matrix and the COD implicit transfer matrix, and determining the actual COD concentration of the target water sample according to the maximum value in the actual COD concentration matrix;
[0068] The total nitrogen hidden transfer matrix is determined by performing photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample total nitrogen concentration matrix constructed by the total nitrogen concentrations of the samples at different concentrations for a preset number of times, and calculating based on the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations;
[0069] The COD latent transfer matrix is obtained by performing photoelectric detection on sample water quality at different concentrations for a preset number of times, and obtaining a sample COD concentration matrix constructed by the sample COD concentrations at different concentrations for a preset number of times, which is determined after calculation based on the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
[0070] In step 101, the water quality indicators include total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration, and the different wavelengths correspond to photoelectric detection of different water quality indicators, including: photoelectric detection of total phosphorus corresponds to a wavelength of 700nm; photoelectric detection of total nitrogen corresponds to a wavelength of 220nm; photoelectric detection of COD corresponds to a wavelength of 440nm; photoelectric detection of ammonia nitrogen corresponds to a wavelength of 700nm.
[0071] For the target water sample, after the following steps are performed in sequence, a preset number of photoelectric detections are performed continuously: first, the target water sample is introduced into the detection pool of the microfluidic chip, the volume of the water sample is accurately controlled in the detection pool, a predetermined amount of chemical reagents is mixed with the water sample to produce a detectable reaction, the mixed water sample is transferred to an appropriate detection area, and the chemical substances in the water sample are colored by a centrifugal process for optical detection. After centrifugal color development, four light sources with different wavelengths (total phosphorus: 700nm; total nitrogen: 220nm; COD: 440nm; ammonia nitrogen: 700nm) are used to continuously perform photoelectric detection on the target water sample, and the number of detections is preset to M times, and the corresponding absorbance value is recorded for each detection, so as to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration of the preset number of times.
[0072] In an optional embodiment, an unknown target water sample is taken and digested, transferred, pre-reagent mixed, and colored in four independent chips, and then photoelectric detection is performed continuously M times, and the concentration value of the signal after photoelectric detection is recorded. The matrix p of the total nitrogen concentration value has a size of [1*M], and the matrix is [p1 p2...pM], the matrix c of the COD concentration value has a size of [1*M], and the matrix is [c1c2...cM], the matrix v of the ammonia nitrogen concentration value has a size of [1*M], and the matrix is [v1 v 2...vM], and the matrix b of the total phosphorus concentration value has a size of [1*M], and the matrix is [b1 b2...bM].
[0073] In step 102, for the total phosphorus concentration, the total phosphorus concentration values for a preset number of times are arithmetic averaged to obtain the concentration mean, which is used as the actual total phosphorus concentration of the target water sample; for the ammonia nitrogen concentration, the ammonia nitrogen concentration values for a preset number of times are arithmetic averaged to obtain the concentration mean, which is used as the actual ammonia nitrogen concentration of the target water sample.
[0074] In step 103, the total nitrogen concentration values of a preset number of times are combined into an initial total nitrogen concentration matrix, and the total nitrogen implicit transfer matrix is calculated by iterative reweighted least squares method based on the known concentration change data determined by multiple tests of standard water samples at different concentrations. The initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix are used to calculate the actual total nitrogen concentration matrix through mathematical transformation, and the maximum value is selected from the actual total nitrogen concentration matrix as the actual total nitrogen concentration of the target water sample.
[0075] Furthermore, the COD concentration values of a preset number of times are combined into an initial COD concentration matrix. Similarly, the COD implicit transfer matrix is calculated by iterative reweighted least squares method based on the known concentration change data. The initial COD concentration matrix and the COD implicit transfer matrix are used to calculate the actual COD concentration matrix through mathematical transformation. The maximum value is selected from the actual COD concentration matrix as the actual COD concentration of the target water sample.
[0076] Those skilled in the art understand that after completing the processes of digestion, quantification, pre-reagent mixing, color development, etc. of different water quality indicators, the detection pool of the microfluidic chip is continuously subjected to photoelectric detection for multiple times. In the four microfluidic water quality detection processes of total phosphorus, ammonia nitrogen, total nitrogen, and COD, the influencing factors of different indicators are different: for total nitrogen, because total nitrogen is detected under a 220nm light source, and 220nm has strong penetrability, any error in the microfluidic chip processing technology, the surface process of the inner cavity flow channel, and the degree of quartz sheet cleaning will eventually be detected by the 220nm light source, and finally superimposed on the total nitrogen absorbance, thereby causing concentration distortion; for COD, its influence comes from the potassium dichromate K2Cr2O7 in the COD reagent, which will continuously react with the microfluidic chip material, and the absorbance detected under the 440nm light source will continue to decrease; while for total phosphorus and ammonia nitrogen, the microfluidic process is the same as that of the single-indicator microfluidic chip, so there is no influence.
[0077] In order to further reflect the technical problem to be solved by this application, a specific analysis is made here combining the similarities and differences between single indicator detection and multi-indicator synchronous detection:
[0078] When performing single indicator testing:
[0079] Total phosphorus detection includes: sampling--quantification--mixing preset reagent A--mixing preset reagent B--transfer--centrifugal color development--photoelectric detection; ammonia nitrogen detection includes: sampling--quantification--mixing preset reagent A--mixing preset reagent B--transfer--centrifugal color development--photoelectric detection; total nitrogen detection includes: sampling--quantification--mixing preset reagent A--transfer--photoelectric detection; COD detection includes: sampling--transfer--photoelectric detection.
[0080] The multi-index simultaneous detection includes: sampling--quantification--mixing of preset reagent A--mixing of preset reagent B--transfer--centrifugal color development--photoelectric detection.
[0081] It can be seen from the above that the above detection has the greatest impact on the total nitrogen and COD indicators, prolonging the contact time between the total nitrogen and COD and the disc chip material, which makes the detection results of the total nitrogen and COD indicators inaccurate. For the problems in the process of detecting water quality parameters by the above microfluidic chip, such as Figure 2As shown, the present invention uses a circular microfluidic chip as a carrier, and the chip is composed of 4 independent fan-shaped chips for total phosphorus, total nitrogen, COD, and ammonia nitrogen. Four different wavelength light emission / reception are used as multi-light source synchronous detection hardware, total phosphorus: 700nm; total nitrogen: 220nm; COD: 440nm; ammonia nitrogen: 700nm; by pre-setting different types of concentration change data, the multi-indicator synchronous detection process is run to calculate the implicit transfer matrix; after the four water samples independently complete digestion, transfer, preset reagent mixing, and color development, multiple photoelectric detections are performed, and the photoelectric detection signal values are recorded; according to the measured unknown water samples, the real estimation of the unknown water samples is calculated through the implicit transfer matrix; through the absorbance change rate of the insensitive chemical reagents of total phosphorus and ammonia nitrogen, it is determined whether the current estimated value comes from the error of the synchronization of the multi-indicator process. If the change rate is large, the error source does not belong to the error distortion value in the process of integrating multiple indicators with a single indicator.
[0082] Optionally, before calculating the actual total nitrogen concentration matrix based on the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, the total nitrogen implicit transfer matrix is determined by calculating based on the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations:
[0083]
[0084] Array, Q is the total nitrogen standard solution matrix at different concentrations.
[0085] Optionally, the sample total nitrogen concentration matrix P is:
[0086]
[0087] The total nitrogen standard solution matrix Q at different concentrations is:
[0088]
[0089] The total nitrogen implicit transfer matrix for:
[0090]
[0091] M is the preset number, and Z is the number of different concentrations.
[0092] Optionally, before constructing an initial total nitrogen concentration matrix according to a preset number of total nitrogen concentrations, the method further includes: performing photoelectric detection of total nitrogen standard solutions at different concentrations for a preset number of times, each photoelectric detection lasting a preset time, and determining the concentration of a photoelectric signal corresponding to the photoelectric detection as the total nitrogen concentration, until the total nitrogen concentration of the preset number of times is obtained; the different concentrations are different concentrations with uniform values. In an optional embodiment, a standard water sample with a uniform total nitrogen concentration distribution is taken to calculate the implicit transfer matrix of the total nitrogen. Taking the range of 0-5 mg / L as an example, examples of uniformly taking the concentration Z are as follows: 0.5 mg / L, 1.0 mg / L, 1.5 mg / L, 2 mg / L, 2.5 mg / L, 3 mg / L, 3.5 mg / L, 4 mg / L, 4.5 mg / L, 5 mg / L. For each group of concentration point standard liquids, M groups of continuous photoelectric detections are performed, and the photoelectric detection time of each group lasts for t seconds. The concentration of each group of photoelectric signals is calculated by calculating the arithmetic mean. The number of concentration value calculations for each group is M, and the number of different concentration points is Z. Finally, Z×M groups of concentration values P can be measured, and the matrix size of P is [Z×M]. The concentrations of the Z groups of standard liquids are stored on the diagonal. The matrix size of the total nitrogen standard liquid matrix Q is [Z×Z]. The iterative reweighted least squares method is used to calculate the implicit transfer matrix of the total nitrogen
[0093] Optionally, before calculating the actual COD concentration matrix based on the initial COD concentration matrix and the COD implicit transfer matrix, the COD implicit transfer matrix is determined after calculation based on the sample COD concentration matrix and the COD standard solution matrix at different concentrations:
[0094]
[0095] degree matrix, H is the COD standard solution matrix at different concentrations.
[0096] Optionally, the sample COD concentration matrix C is:
[0097]
[0098] The COD standard solution matrix H at different concentrations is:
[0099]
[0100] The COD implicit transfer matrix ω is:
[0101]
[0102] M is the preset number, and Z is the number of different concentrations.
[0103] Optionally, take a standard water sample with uniform COD concentration distribution, and calculate the COD implicit transfer matrix ω in the same way, with a matrix size of [M×Z].
[0104] Optionally, after determining the actual COD concentration of the target water sample according to the maximum value in the actual COD concentration matrix, the method further includes:
[0105] Calculate the target total phosphorus concentration variance based on the total phosphorus concentration of the preset times, and calculate the target ammonia nitrogen concentration variance based on the ammonia nitrogen concentration of the preset times;
[0106] When the target total phosphorus concentration variance is within the preset total phosphorus concentration variance interval, and the target ammonia nitrogen concentration variance is within the preset ammonia nitrogen concentration variance interval, the actual total nitrogen concentration and the actual COD concentration of the target water sample are determined to be valid calculation results; otherwise, the actual total nitrogen concentration and the actual COD concentration of the target water sample are determined to be invalid calculation results.
[0107] Optionally, the target total phosphorus concentration variance is calculated using a preset variance formula And the target ammonia nitrogen concentration variance The estimates of total nitrogen and COD are valid if the following conditions are met at the same time:
[0108]
[0109]
[0110] in, is the minimum variance of total phosphorus concentration in samples, is the maximum variance of total phosphorus concentration in samples, is the minimum variance of the sample ammonia nitrogen concentration, is the maximum variance of the sample ammonia nitrogen concentration.
[0111] Optionally, before calculating the target total phosphorus concentration variance according to the total phosphorus concentration of a preset number of times and calculating the target ammonia nitrogen concentration variance according to the ammonia nitrogen concentration of a preset number of times, the method further includes:
[0112] Performing photoelectric detection on the sample water quality for a preset number of times to obtain the total phosphorus concentration of the sample at different concentrations for a preset number of times, and performing photoelectric detection on the sample water quality for a preset number of times to obtain the ammonia nitrogen concentration of the sample at different concentrations for a preset number of times;
[0113] For each concentration, according to the total phosphorus concentrations of all samples at the concentration, the variance of the total phosphorus concentration of the sample is calculated, all concentrations are traversed, the variance of the total phosphorus concentration of the sample at each concentration is determined, and the preset total phosphorus concentration variance interval is determined according to the maximum and minimum variances of the total phosphorus concentration of the sample at all concentrations;
[0114] For each concentration, the variance of the sample ammonia nitrogen concentration is calculated based on the ammonia nitrogen concentrations of all samples at the concentration, all concentrations are traversed to determine the variance of the sample ammonia nitrogen concentration at each concentration, and the preset ammonia nitrogen concentration variance interval is determined based on the maximum and minimum values of the variance of the sample ammonia nitrogen concentrations at all concentrations.
[0115] Optionally, take a standard water sample with uniform concentration distribution of total phosphorus and ammonia nitrogen indicators, calculate the maximum and minimum variance range of the standard solution concentration, and set the matrix of ammonia nitrogen concentration of the preset number of samples at different concentrations as:
[0116]
[0117] The formula for finding the variance of the first row of data is:
[0118]
[0119] Among them, V ar1 is the variance of the first row of data, V 1.i is the i-th data in the first row, is the mean of the first row of data, M is the number of the first row of data, that is, the preset number of times. Traverse all rows and get the variance corresponding to all rows:
[0120]
[0121] Among them, Z is the number of rows of the matrix of the ammonia nitrogen concentration of the samples at different concentrations. The minimum variance of the total phosphorus concentration of the samples is determined from the above data. And the maximum variance of total phosphorus concentration of samples Determine the preset total phosphorus concentration variance interval based on the maximum and minimum total phosphorus concentration variance of samples at all concentrations Similarly, determine the minimum variance of the sample ammonia nitrogen concentration And the maximum variance of sample ammonia nitrogen concentration Determine the preset ammonia nitrogen concentration variance interval based on the maximum and minimum ammonia nitrogen concentration variance of the samples at all concentrations
[0122] Figure 4It is a trend diagram of changes in different standard liquid points provided by the present invention. The present invention aims to upgrade the single-indicator microfluidic chip detection to the water quality concentration detection of four indicators. In the execution process of the four indicators, there are many overlapping action processes, such as sampling, transfer, and photoelectric detection, and the four indicators can more completely represent the water quality characteristics of water at a sampling point. However, the integration of these four indicators also has its defects, that is, the COD indicator and the total nitrogen indicator prolong the contact time between the chemical reagent and the microfluidic chip material. This results in distortion in the photoelectric detection of COD and total nitrogen after all four indicators have completed the transfer and color development. If the photoelectric detection signal value is distorted, the absorbance value is distorted, and the concentration value converted is also distorted.
[0123] In order to solve this technical problem, the present invention estimates the true concentration value through multiple photoelectric detection values. The time of multiple photoelectric detections is actually an extension of the latent change process, and the initial true value is calculated by observing the subsequent changes. Through experiments, it can be found that the longer the COD and total nitrogen stay in the chip, the greater the concentration value gradually becomes, and the change range of low concentration is greater than that of high concentration. Finally, they gradually approach a certain concentration value and no longer change.
[0124] On the other hand, the changes in total phosphorus and ammonia nitrogen are not obvious, and they are basically a straight line that is relatively stable. Because the multi-indicator process is exactly the same as the single-indicator process of total phosphorus and ammonia nitrogen, the absorbance changes of total phosphorus and ammonia nitrogen can be used to reflect whether the calculation of multiple indicators is reasonable. If the concentration value errors of total phosphorus and ammonia nitrogen in multiple photoelectric detections deviate greatly, indicating that other variables are introduced (disc chip material, cleanliness, light signal pollution, etc.), then this calculation method cannot meet the requirements. The present invention can analyze the influence deviation caused by the prolonged contact time of COD and total nitrogen with microfluidic chip materials in the process of synchronous detection from single indicator to multi-indicator.
[0125] like Figure 4 As shown, the larger the Z value, the closer the estimated concentration value is to the true concentration value, and the larger the M value, the more stable the calculated value change. For example, when Z=10, M=8, the true concentration is 1.25 mg / L, and the estimated concentration is 1.30-1.4; when Z=15, M=8, the true concentration is 1.25 mg / L, and the estimated concentration is 1.265-1.365; when Z=15, M=12, the true concentration is 1.25 mg / L, and the estimated concentration is 1.265-1.295. To ensure that no singular values appear when the matrix is inverted, Z≥M is set. In an optional embodiment, Z=6, M=6:
[0126]
[0127]
[0128] Total nitrogen implicit transfer matrix
[0129]
[0130] In order to improve the utilization efficiency of the microfluidic chip, the present invention integrates the detection of multiple different indicators on one chip. When the microfluidic chip is used to detect the water quality concentration, in the process of synchronous centrifugal transfer of multiple indicators and mixing of pre-set reagents, different chemical reagents have different reaction sensitivities to the microfluidic chip material, resulting in abnormal distortion of the water quality detection concentration. In order to be compatible with the detection processes of different indicators and make the final detection concentration result as accurate as when four independent microfluidic chips are detected separately, the present invention proposes a calculation method for restoring the actual water quality concentration using an implicit transfer matrix, thereby improving the accuracy of the detection results of the total nitrogen concentration and the COD concentration. The total phosphorus concentration and the ammonia nitrogen concentration are not obviously sensitive to the reaction of the microfluidic chip material during detection, so there is no need to consider the change effect of the change in the photoelectric detection time on the detection result. Finally, when the detection of multiple different indicators is integrated on the same chip, the detection results of the total nitrogen concentration, the COD concentration, the total phosphorus concentration and the ammonia nitrogen concentration are all very accurate, thereby shortening the detection time and improving the detection efficiency.
[0131] Figure 2 This is one of the structural schematic diagrams of the water quality detection concentration calculation system provided by the present invention, wherein the water quality detection concentration calculation system is a microfluidic chip, and the microfluidic chip is used for:
[0132] For the target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, the target water sample is continuously subjected to photoelectric detection for a preset number of times to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration for the preset number of times, wherein different wavelengths correspond to photoelectric detection of different water quality indicators;
[0133] Determine the actual total phosphorus concentration of the target water sample according to the concentration average of the total phosphorus concentrations of the preset times, and determine the actual ammonia nitrogen concentration of the target water sample according to the concentration average of the ammonia nitrogen concentrations of the preset times;
[0134] An initial total nitrogen concentration matrix is constructed according to the total nitrogen concentrations of a preset number of times, an actual total nitrogen concentration matrix is calculated according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and the actual total nitrogen concentration of the target water sample is determined according to the maximum value in the actual total nitrogen concentration matrix; an initial COD concentration matrix is constructed according to the COD concentrations of a preset number of times, an actual COD concentration matrix is calculated according to the initial COD concentration matrix and the COD implicit transfer matrix, and the actual COD concentration of the target water sample is determined according to the maximum value in the actual COD concentration matrix;
[0135] The total nitrogen hidden transfer matrix is determined by performing photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample total nitrogen concentration matrix constructed by the total nitrogen concentrations of the samples at different concentrations for a preset number of times, and calculating based on the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations;
[0136] The COD latent transfer matrix is obtained by performing photoelectric detection on sample water quality at different concentrations for a preset number of times, and obtaining a sample COD concentration matrix constructed by the sample COD concentrations at different concentrations for a preset number of times, which is determined after calculation based on the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
[0137] Figure 3 This is the second structural diagram of the water quality detection concentration calculation system provided by the present invention, such as Figure 2 as well as Figure 3 As shown, in order to realize the calculation of water quality concentration for multi-index detection, the present invention designs a circular microfluidic disc chip. The overall manufacturing process of the microfluidic chip is divided into mold injection parts, PMMA detection sheet upper, PMMA detection sheet lower, quartz detection sheet upper, quartz detection sheet lower, circular pressure-sensitive film, bonding double-sided tape and other parts.
[0138] Based on the existing design, this application splices a single fan-shaped chip into a circular chip. The above seven materials will be shared in different indicator processes. Among them, the PMMA detection sheet is bonded to the upper and lower layers of three detection cavities of the microfluidic chip by bonding double-sided adhesive, which is used for the concentration detection of ammonia nitrogen, total phosphorus, and COD; the quartz sheet detection sheet is bonded to one of the detection cavities of the upper and lower layers of the detection cavity of the microfluidic chip by bonding double-sided adhesive, which is used for the total nitrogen concentration detection. The bottom pressure-sensitive film of the microfluidic chip is hot-pressed to form a seal. Optionally, four different wavelength light emission / reception is multi-channel light source asynchronous detection hardware, total phosphorus 700nm; total nitrogen 220nm; COD440nm; ammonia nitrogen 700nm. On the basis of the existing technology, a single indicator is expanded into four different indicators, and the implicit transfer matrix is calculated by presetting different types of concentration change data.
[0139] In order to improve the utilization efficiency of the microfluidic chip, the present invention integrates the detection of multiple different indicators on one chip. When the microfluidic chip is used to detect the water quality concentration, in the process of synchronous centrifugal transfer of multiple indicators and mixing of pre-set reagents, different chemical reagents have different reaction sensitivities to the microfluidic chip material, resulting in abnormal distortion of the water quality detection concentration. In order to be compatible with the detection processes of different indicators and make the final detection concentration result as accurate as when four independent microfluidic chips are detected separately, the present invention proposes a calculation method for restoring the actual water quality concentration using an implicit transfer matrix, thereby improving the accuracy of the detection results of the total nitrogen concentration and the COD concentration. The total phosphorus concentration and the ammonia nitrogen concentration are not obviously sensitive to the reaction of the microfluidic chip material during detection, so there is no need to consider the change effect of the change in the photoelectric detection time on the detection result. Finally, when the detection of multiple different indicators is integrated on the same chip, the detection results of the total nitrogen concentration, the COD concentration, the total phosphorus concentration and the ammonia nitrogen concentration are all very accurate, thereby shortening the detection time and improving the detection efficiency.
[0140] Figure 5 Schematic diagram of the structure of the electronic device provided by the present invention. Figure 5As shown, the electronic device may include: a processor (processor) 510, a communication interface (Communications Interface) 520, a memory (memory) 530 and a communication bus 540, wherein the processor 510, the communication interface 520, and the memory 530 communicate with each other through the communication bus 540. The processor 510 can call the logic instructions in the memory 530 to execute the water quality detection concentration calculation method, which includes: for the target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, the target water sample is continuously photoelectrically detected for a preset number of times to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration of the preset number of times, wherein different wavelengths correspond to the photoelectric detection of different water quality indicators; the actual total phosphorus concentration of the target water sample is determined according to the concentration mean of the total phosphorus concentration of the preset number of times, and the actual ammonia nitrogen concentration of the target water sample is determined according to the concentration mean of the ammonia nitrogen concentration of the preset number of times; an initial total nitrogen concentration matrix is constructed according to the total nitrogen concentration of the preset number of times, the actual total nitrogen concentration matrix is calculated according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and the actual total nitrogen concentration of the target water sample is determined according to the maximum value in the actual total nitrogen concentration matrix. degree; construct an initial COD concentration matrix according to the COD concentrations of a preset number of times, calculate the actual COD concentration matrix according to the initial COD concentration matrix and the COD hidden transfer matrix, and determine the actual COD concentration of the target water sample according to the maximum value in the actual COD concentration matrix; the total nitrogen hidden transfer matrix is a photoelectric detection of sample water quality at different concentrations for a preset number of times, and a sample total nitrogen concentration matrix constructed by the sample total nitrogen concentrations of the preset number of times at different concentrations is obtained, which is determined after calculation according to the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations; the COD hidden transfer matrix is a photoelectric detection of sample water quality at different concentrations for a preset number of times, and a sample COD concentration matrix constructed by the sample COD concentrations of the preset number of times at different concentrations is obtained, which is determined after calculation according to the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
[0141] In addition, the logic instructions in the above-mentioned memory 530 can be implemented in the form of a software functional unit and can be stored in a computer-readable storage medium when it is sold or used as an independent product. Based on such an understanding, the technical solution of the present invention, in essence, or the part that contributes to the prior art or the part of the technical solution, can be embodied in the form of a software product, and the computer software product is stored in a storage medium, including a number of instructions for a computer device (which can be a personal computer, a server, or a network device, etc.) to perform all or part of the steps of the method described in each embodiment of the present invention. The aforementioned storage medium includes: U disk, mobile hard disk, read-only memory (ROM, Read-Only Memory), random access memory (RAM, Random Access Memory), disk or optical disk, etc. Various media that can store program codes.
[0142] On the other hand, the present invention also provides a computer program product, which includes a computer program. The computer program can be stored on a non-transitory computer-readable storage medium. When the computer program is executed by a processor, the computer can execute a water quality detection concentration calculation method provided by the above methods, the method comprising: for a target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, continuously performing photoelectric detection of the target water sample for a preset number of times to obtain a preset number of total phosphorus concentrations, total nitrogen concentrations, COD concentrations and ammonia nitrogen concentrations, wherein different wavelengths correspond to photoelectric detections of different water quality indicators; determining the actual total phosphorus concentration of the target water sample according to the concentration mean of the preset number of total phosphorus concentrations, and determining the actual ammonia nitrogen concentration of the target water sample according to the concentration mean of the preset number of ammonia nitrogen concentrations; constructing an initial total nitrogen concentration matrix according to the total nitrogen concentrations of the preset number of times, and calculating the actual total nitrogen according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix. concentration matrix, determining the actual total nitrogen concentration of the target water sample according to the maximum value in the actual total nitrogen concentration matrix; constructing an initial COD concentration matrix according to the COD concentrations of a preset number of times, calculating the actual COD concentration matrix according to the initial COD concentration matrix and the COD hidden transfer matrix, and determining the actual COD concentration of the target water sample according to the maximum value in the actual COD concentration matrix; the total nitrogen hidden transfer matrix is a photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample total nitrogen concentration matrix constructed by the sample total nitrogen concentrations of the preset number of times at different concentrations, and is determined after calculation according to the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations; the COD hidden transfer matrix is a photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample COD concentration matrix constructed by the sample COD concentrations of the preset number of times at different concentrations, and is determined after calculation according to the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
[0143] On the other hand, the present invention also provides a non-transitory computer-readable storage medium having a computer program stored thereon, which, when executed by a processor, is implemented to execute the water quality detection concentration calculation method provided by the above-mentioned methods, the method comprising: for a target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, continuously performing photoelectric detection of the target water sample for a preset number of times to obtain a total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration for a preset number of times, wherein different wavelengths correspond to photoelectric detection of different water quality indicators; determining the actual total phosphorus concentration of the target water sample according to the concentration mean of the total phosphorus concentration for a preset number of times, and determining the actual ammonia nitrogen concentration of the target water sample according to the concentration mean of the ammonia nitrogen concentration for a preset number of times; constructing an initial total nitrogen concentration matrix according to the total nitrogen concentration for a preset number of times, calculating the actual total nitrogen concentration matrix according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and calculating the actual total nitrogen concentration matrix according to the actual total nitrogen concentration matrix The actual total nitrogen concentration of the target water sample is determined by the maximum value in the matrix; an initial COD concentration matrix is constructed according to the COD concentrations of a preset number of times, and the actual COD concentration matrix is calculated according to the initial COD concentration matrix and the COD hidden transfer matrix, and the actual COD concentration of the target water sample is determined according to the maximum value in the actual COD concentration matrix; the total nitrogen hidden transfer matrix is obtained by performing photoelectric detection on the sample water quality at different concentrations for a preset number of times, and a sample total nitrogen concentration matrix constructed by the sample total nitrogen concentrations of the preset number of times at different concentrations is obtained, and the total nitrogen standard solution matrix at different concentrations is calculated and determined; the COD hidden transfer matrix is obtained by performing photoelectric detection on the sample water quality at different concentrations for a preset number of times, and a sample COD concentration matrix constructed by the sample COD concentrations of the preset number of times at different concentrations is obtained, and the COD standard solution matrix at different concentrations is calculated and determined.
[0144] The device embodiments described above are merely illustrative, wherein the units described as separate components may or may not be physically separated, and the components displayed as units may or may not be physical units, that is, they may be located in one place, or they may be distributed on multiple network units. Some or all of the modules may be selected according to actual needs to achieve the purpose of the scheme of this embodiment. Ordinary technicians in this field can understand and implement it without paying creative labor.
[0145] Through the description of the above implementation methods, those skilled in the art can clearly understand that each implementation method can be implemented by means of software plus a necessary general hardware platform, and of course, it can also be implemented by hardware. Based on this understanding, the above technical solution is essentially or the part that contributes to the prior art can be embodied in the form of a software product, and the computer software product can be stored in a computer-readable storage medium, such as ROM / RAM, a disk, an optical disk, etc., including a number of instructions for a computer device (which can be a personal computer, a server, or a network device, etc.) to execute the methods described in each embodiment or some parts of the embodiments.
[0146] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for calculating water quality detection concentration, characterized in that: include: For the target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, the target water sample is continuously subjected to photoelectric detection for a preset number of times to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration for the preset number of times, wherein different wavelengths correspond to photoelectric detection of different water quality indicators; Determine the actual total phosphorus concentration of the target water sample according to the concentration average of the total phosphorus concentrations of the preset times, and determine the actual ammonia nitrogen concentration of the target water sample according to the concentration average of the ammonia nitrogen concentrations of the preset times; An initial total nitrogen concentration matrix is constructed according to the total nitrogen concentrations of a preset number of times, an actual total nitrogen concentration matrix is calculated according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and the actual total nitrogen concentration of the target water sample is determined according to the maximum value in the actual total nitrogen concentration matrix; an initial COD concentration matrix is constructed according to the COD concentrations of a preset number of times, an actual COD concentration matrix is calculated according to the initial COD concentration matrix and the COD implicit transfer matrix, and the actual COD concentration of the target water sample is determined according to the maximum value in the actual COD concentration matrix; The total nitrogen hidden transfer matrix is determined by performing photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample total nitrogen concentration matrix constructed by the total nitrogen concentrations of the samples at different concentrations for a preset number of times, and calculating based on the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations; The COD latent transfer matrix is obtained by performing photoelectric detection on sample water quality at different concentrations for a preset number of times, and obtaining a sample COD concentration matrix constructed by the sample COD concentrations at different concentrations for a preset number of times, which is determined after calculation based on the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
2. The water quality detection concentration calculation method according to claim 1, characterized in that: Before calculating the actual total nitrogen concentration matrix based on the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, the total nitrogen implicit transfer matrix is determined by calculating the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations: in, is the total nitrogen implicit transfer matrix, P T is the transpose of P, P is the total nitrogen concentration matrix of the samples, and Q is the total nitrogen standard solution matrix at different concentrations.
3. The water quality detection concentration calculation method according to claim 2 is characterized in that: The sample total nitrogen concentration matrix P is: The total nitrogen standard solution matrix Q at different concentrations is: The total nitrogen implicit transfer matrix for: M is the preset number, and Z is the number of different concentrations.
4. The water quality detection concentration calculation method according to claim 1 is characterized in that: Before calculating the actual COD concentration matrix based on the initial COD concentration matrix and the COD implicit transfer matrix, the COD implicit transfer matrix is determined by calculating the sample COD concentration matrix and the COD standard solution matrix at different concentrations: Among them, ω is the COD implicit transfer matrix, C T is the transpose of C, C is the sample COD concentration matrix, and H is the COD standard solution matrix at different concentrations.
5. The water quality detection concentration calculation method according to claim 4 is characterized in that: The sample COD concentration matrix C is: The COD standard solution matrix H at different concentrations is: The COD implicit transfer matrix ω is: M is the preset number, and Z is the number of different concentrations.
6. The water quality detection concentration calculation method according to claim 1, characterized in that: After determining the actual COD concentration of the target water sample according to the maximum value in the actual COD concentration matrix, the method further includes: Calculate the target total phosphorus concentration variance based on the total phosphorus concentration of the preset times, and calculate the target ammonia nitrogen concentration variance based on the ammonia nitrogen concentration of the preset times; When the target total phosphorus concentration variance is within the preset total phosphorus concentration variance interval, and the target ammonia nitrogen concentration variance is within the preset ammonia nitrogen concentration variance interval, the actual total nitrogen concentration and the actual COD concentration of the target water sample are determined to be valid calculation results; otherwise, the actual total nitrogen concentration and the actual COD concentration of the target water sample are determined to be invalid calculation results.
7. The water quality detection concentration calculation method according to claim 6, characterized in that: Before calculating the target total phosphorus concentration variance according to the total phosphorus concentration of the preset number of times and calculating the target ammonia nitrogen concentration variance according to the ammonia nitrogen concentration of the preset number of times, the method further includes: Performing photoelectric detection on the sample water quality for a preset number of times to obtain the total phosphorus concentration of the sample at different concentrations for a preset number of times, and performing photoelectric detection on the sample water quality for a preset number of times to obtain the ammonia nitrogen concentration of the sample at different concentrations for a preset number of times; For each concentration, according to the total phosphorus concentrations of all samples at the concentration, the variance of the total phosphorus concentration of the sample is calculated, all concentrations are traversed, the variance of the total phosphorus concentration of the sample at each concentration is determined, and the preset total phosphorus concentration variance interval is determined according to the maximum and minimum variances of the total phosphorus concentration of the sample at all concentrations; For each concentration, the variance of the sample ammonia nitrogen concentration is calculated based on the ammonia nitrogen concentrations of all samples at the concentration, all concentrations are traversed to determine the variance of the sample ammonia nitrogen concentration at each concentration, and the preset ammonia nitrogen concentration variance interval is determined based on the maximum and minimum values of the variance of the sample ammonia nitrogen concentrations at all concentrations.
8. The water quality detection concentration calculation method according to claim 1, characterized in that: The water quality indicators include total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration. The different wavelengths correspond to photoelectric detection of different water quality indicators, including: Photoelectric detection of total phosphorus corresponds to a wavelength of 700 nm; Photoelectric detection of total nitrogen corresponds to a wavelength of 220 nm; Photoelectric detection of COD corresponds to a wavelength of 440 nm; The photoelectric detection of ammonia nitrogen corresponds to a wavelength of 700 nm.
9. The water quality detection concentration calculation method according to claim 1, characterized in that: Before constructing an initial total nitrogen concentration matrix according to the total nitrogen concentrations of a preset number of times, the method further includes: Performing photoelectric detection for a preset number of times on the total nitrogen standard solution at different concentrations, each photoelectric detection time lasting for a preset time, and determining the concentration of the photoelectric signal corresponding to the photoelectric detection as the total nitrogen concentration, until the total nitrogen concentration of the preset number of times is obtained; The different concentrations are different concentrations with uniform values.
10. A water quality detection concentration calculation system, characterized in that: The water quality detection concentration calculation system is a microfluidic chip, and the microfluidic chip is used for: For the target water sample, after performing injection, quantification, mixing of preset reagents, transfer and centrifugal color development in sequence, the target water sample is continuously subjected to photoelectric detection for a preset number of times to obtain the total phosphorus concentration, total nitrogen concentration, COD concentration and ammonia nitrogen concentration for the preset number of times, wherein different wavelengths correspond to photoelectric detection of different water quality indicators; Determine the actual total phosphorus concentration of the target water sample according to the concentration average of the total phosphorus concentrations of the preset times, and determine the actual ammonia nitrogen concentration of the target water sample according to the concentration average of the ammonia nitrogen concentrations of the preset times; An initial total nitrogen concentration matrix is constructed according to the total nitrogen concentrations of a preset number of times, an actual total nitrogen concentration matrix is calculated according to the initial total nitrogen concentration matrix and the total nitrogen implicit transfer matrix, and the actual total nitrogen concentration of the target water sample is determined according to the maximum value in the actual total nitrogen concentration matrix; an initial COD concentration matrix is constructed according to the COD concentrations of a preset number of times, an actual COD concentration matrix is calculated according to the initial COD concentration matrix and the COD implicit transfer matrix, and the actual COD concentration of the target water sample is determined according to the maximum value in the actual COD concentration matrix; The total nitrogen hidden transfer matrix is determined by performing photoelectric detection of sample water quality at different concentrations for a preset number of times, obtaining a sample total nitrogen concentration matrix constructed by the total nitrogen concentrations of the samples at different concentrations for a preset number of times, and calculating based on the sample total nitrogen concentration matrix and the total nitrogen standard solution matrix at different concentrations; The COD latent transfer matrix is obtained by performing photoelectric detection on sample water quality at different concentrations for a preset number of times, and obtaining a sample COD concentration matrix constructed by the sample COD concentrations at different concentrations for a preset number of times, which is determined after calculation based on the sample COD concentration matrix and the COD standard solution matrix at different concentrations.
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