Method for rapidly analyzing hydrophilicity and hydrophobicity of dissolved organic matters in water sample of sewage plant based on three-dimensional fluorescence spectrum

Abstract

The invention relates to a method for rapidly analyzing hydrophilicity and hydrophobicity of dissolved organic matters in a water sample of a sewage plant based on a three-dimensional fluorescence spectrum, and belongs to the technical field of environmental monitoring. Measuring the hydrophilic and hydrophobic data and the three-dimensional fluorescence spectrum of the original reference water sample and the amplified water sample, and establishing a reference database of the hydrophilic and hydrophobic data and the three-dimensional fluorescence spectrum of the reference sample; combining the three-dimensional fluorescence spectrum of the to-be-detected water sample with the three-dimensional fluorescence spectrum of the reference sample, and carrying out parallel factor analysis to obtain fluorescent components and scores of all the components; and obtaining hydrophilic and hydrophobic data of the to-be-detected sample according to the correlation between the hydrophilic and hydrophobic data of the sample and the scores of the fluorescent components. If the water quality of the to-be-detected water sample is changed and the parallel factor analysis and detection are not passed, re-amplifying the sample with the changed water quality, and storing the hydrophilic and hydrophobic data, the score of the fluorescent component and other information into a reference sample library.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental monitoring, and in particular relates to a method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples of a sewage plant based on three-dimensional fluorescence spectroscopy. Background Art

[0002] Natural water bodies, sewage plant influent and treated tailwater often contain a large amount of dissolved organic matter, which is the main source of membrane fouling and disinfection by-products in water purification or sewage reuse processes. A large number of studies have shown that the generation of membrane fouling and disinfection by-products is related to the hydrophilicity of dissolved organic matter. In order to monitor and predict membrane fouling and the generation of disinfection by-products in real time, it is necessary to detect and identify the hydrophilicity of dissolved organic matter in water.

[0003] At present, the detection of hydrophilicity of dissolved organic matter usually adopts the method of resin separation and the method of measuring the content of organic matter to carry out quantitative analysis of hydrophilicity of dissolved organic matter. This method is cumbersome and time-consuming. It is also possible to carry out quantitative analysis of hydrophilicity of organic matter by large-scale analytical instruments such as liquid chromatography, but such methods require specific modification of analytical instruments, which requires high capital investment.

[0004] With the development of smart water services, real-time collection and online detection of water quality information are very necessary, and the hydrophilicity of dissolved organic matter in water can help predict the effect of water treatment process, membrane fouling, and the generation of disinfection by-products, etc. Therefore, a low-cost, online analysis method for rapid analysis of the hydrophilicity of dissolved organic matter in water is urgently needed to achieve online detection of dissolved organic matter in water bodies, sewage plant influent, and treatment tail water.

[0005] Spectroscopy, especially three-dimensional fluorescence spectroscopy, has the advantages of simple pre-treatment, non-destructive sample, rapid detection, and the ability to display water quality fingerprint information. It is very suitable for rapid detection of the hydrophilicity of dissolved organic matter in water. However, three-dimensional fluorescence spectroscopy is often used to qualitatively or semi-quantitatively characterize humic acid, fulvic acid and protein substances in dissolved organic matter in water, and the characterization of the hydrophilicity of dissolved organic matter is very limited. Summary of the invention

[0006] In view of the deficiencies of the prior art, the present invention proposes a method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from sewage treatment plants based on three-dimensional fluorescence spectroscopy to solve or improve the above-mentioned problems.

[0007] The present invention adopts the following technical solutions to solve the above problems:

[0008] A method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from a sewage treatment plant based on three-dimensional fluorescence spectroscopy, the method comprising the following steps:

[0009] S1: Select a stable water sample from the sewage plant to be measured as a reference water sample, and amplify the water sample:

[0010] S2: Determine the organic matter content of each amplified sample and the original sample. The hydrophilicity data of all samples are expressed as the ratio of hydrophobic organic matter to total organic matter content:

[0011] S3: Perform three-dimensional fluorescence spectrum analysis on each amplified sample and the original reference sample, remove Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample, and use the Raman peak to standardize the three-dimensional fluorescence spectrum data:

[0012] S4: Add the hydrophilic and hydrophobic organic matter data and three-dimensional fluorescence spectrum data of the reference sample and the amplified sample to the reference database:

[0013] S5: Take an unknown water sample to be tested, measure its three-dimensional fluorescence spectrum, remove Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample, and use the Raman peak to standardize the three-dimensional fluorescence spectrum data:

[0014] S6: The three-dimensional fluorescence spectrum of the sample to be tested is combined with the three-dimensional fluorescence spectrum data of the reference database, and the three-dimensional fluorescence spectrum is decomposed using the parallel factor method. To ensure the stability of the model, the model is constructed by setting multiple factor numbers to minimize the residual and maximize the kernel consistency, and to meet the split-half test:

[0015] S7; According to the parallel factor model, the location of each fluorescent component and the maximum fluorescence intensity of the component are obtained:

[0016] S8: Based on the correlation between the maximum fluorescence intensity of each component and the hydrophilicity and hydrophobicity data of the reference sample, the hydrophilicity and hydrophobicity data of the unknown sample to be tested are obtained.

[0017] Furthermore, in S1, the water sample amplification is specifically to use XAD-8 resin to adsorb hydrophobic organic components and change the content of organic components in the sample, and the steps include:

[0018] S101: Collect and select a water sample with stable water quality from the sewage treatment plant to be measured as a reference water sample, and pass the collected water sample through a 0.45 μm filter membrane to remove impurities and suspended matter;

[0019] S102: Activate the XAD-8 resin with cyclohexane and methanol, then wash it with ultrapure water, and load 10 mL of the washed XAD-8 resin into the chromatography column;

[0020] S103: using a peristaltic pump to continuously inject the water sample into the chromatography column, the flow rate of the peristaltic pump is 3 mL / min;

[0021] S104: Continuously collect the effluent from the chromatography column as amplification samples. The volume of each amplification sample is equal to the volume of the resin, and the samples are numbered consecutively according to the multiple of the resin volume.

[0022] Furthermore, in S2, the method for determining the organic matter content of the amplified sample and the original sample is to determine it by measuring the dissolved organic carbon or chemical oxygen demand of the sample.

[0023] Furthermore, in the determination method, the hydrophilicity data of all samples are expressed by the ratio of hydrophobic organic matter to total organic matter content, and the calculation formula is:

[0024]

[0025] Among them, H i is the hydrophilicity of the i-th sample, C1, C i and C0 are the organic matter concentrations of the first and i-th amplified samples and raw water, respectively; if raw water H is calculated, then C i It's C0.

[0026] Furthermore, in S3, the Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample can be removed by a subtraction method or an interpolation method.

[0027] Furthermore, the subtraction method directly deletes the Raman or Rayleigh scattering fluorescence data, and the interpolation method uses the cubic spline interpolation method to fit the normal fluorescence signal intensity on both sides of the Rayleigh scattering band, thereby eliminating the abnormal fluorescence value caused by Rayleigh scattering; the three-dimensional fluorescence data standardization is to standardize each fluorescence data of the three-dimensional fluorescence spectrum by the integral area of ​​the pure water Raman peak at the excitation wavelength of 350nm.

[0028] Furthermore, S6 specifically includes the following steps:

[0029] S601: merging the reference data and the three-dimensional fluorescence data of the water sample to be tested, and forming the three-dimensional fluorescence data of i samples into a three-dimensional data matrix of M*N*I;

[0030] S602: Using the trilinear principle of the parallel factor method, the matrix X is decomposed into F factors. Then the original matrix X can be expressed as:

[0031]

[0032] Among them, F represents the number of factors, a m,f represents the vector a f The mth element in a m,f 、b n,f and c i,f Construct matrices A, B, C, x respectively m,n,i(m=1,…,M,n=1,…,N,i=1,…,I) is a three-dimensional data matrix X of M*N*I, e m,n,i (m=1,…,M,n=1,…,N,i=1,…,I) is the three-dimensional error matrix E of M*N*I;

[0033] S603: The three matrices A, B and C decomposed from the matrix X are respectively a score matrix, i.e., a relative mass concentration matrix A of each component, a load matrix B corresponding to the emission spectrum, and a load matrix C corresponding to the excitation spectrum.

[0034] S604: According to formula (2), multiple F values ​​are set, and A is calculated for each F value through loop iteration. T , B T , C T The least squares estimate is performed until E converges to the minimum and the kernel consistency is the highest. At this time, the F value is the optimal value. At this time, the three-dimensional fluorescence data of the sample set can be decomposed into F factors according to the parallel factor method, and the parallel factor model under this time is the optimal model.

[0035] S605: Perform a random split-half test on the established parallel factor model to examine whether the model can pass the split-half test:

[0036] If the established parallel factor model satisfies the split-half test, proceed to the subsequent process;

[0037] If the established parallel factor model does not satisfy the split-half test, the sample to be tested is used as a new reference sample, sample amplification is performed, and the organic matter concentration and three-dimensional fluorescence spectrum are analyzed and included in the reference database, that is, the sample to be tested repeats steps S1 to S4.

[0038] Advantages of the present invention:

[0039] The present invention utilizes XAD-8 resin to amplify the reference water sample of the sewage plant water sample to be tested, and based on the matlab2022b software platform, uses the parallel factor analysis method to analyze the three-dimensional fluorescence spectrum data set composed of the reference water sample and the water sample to be tested, so as to obtain the spectral position and fluorescence intensity information of the main fluorescence components, and obtain the hydrophilicity characteristic information of the sample to be tested through the linear relationship between the fluorescence intensity and the concentration of the hydrophilic and hydrophobic components. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The exemplary embodiments of the present invention are described in more detail with reference to the accompanying drawings, so that the above-mentioned objects, features and advantages of the present invention become more apparent. In the exemplary embodiments of the present invention, the same reference numerals generally represent the same components.

[0041] Figure 1 It is a technical flow chart of the present invention;

[0042] Figure 2This is the EEM image of the reference sample from the sewage plant after treatment;

[0043] Figure 3 (a) is the EEM image of the sample (sample 1) after treatment during the stable period of water quality in the sewage treatment plant;

[0044] Figure 3 (b) is the EEM image of the sample (sample 2) after treatment during the period of water quality fluctuation in the sewage plant;

[0045] Figure 4 This is the result of parallel factor analysis of the sample (sample 1) during the period of stable water quality;

[0046] Figure 5 This is the result of parallel factor analysis for the sample during the period of water quality fluctuation (sample 2);

[0047] Figure 6 For multiple sewage plant samples F max Correlation diagram with hydrophilicity;

[0048] Figure 7 This is a graph showing the relationship between the rapid test results of the hydrophilicity and hydrophobicity of multiple samples from the same sampling port of a sewage treatment plant and the actual measurements. DETAILED DESCRIPTION

[0049] The specific implementation modes of the present invention are described below to facilitate the understanding of the present invention by those skilled in the art. However, it should be clear that the present invention is not limited to the scope of the specific implementation modes. For those skilled in the art, the main various changes are within the spirit and scope of the present invention as defined and determined by the attached claims. These changes are obvious, and all inventions and creations utilizing the concept of the present invention are protected.

[0050] It should be noted that the professional terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Unless otherwise specifically stated, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be purchased from the market or prepared by existing methods.

[0051] According to an embodiment of the present application, the specific process is as follows: Figure 1 The method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in sewage plant water samples based on three-dimensional fluorescence spectroscopy in this scheme includes:

[0052] S1. Select a water sample from a stable sewage treatment plant to be tested as a reference water sample, and amplify the water sample using XAD-8 resin;

[0053] S2. Determine the organic matter content of each amplified sample and the original sample, and the hydrophilicity data of all samples are expressed as the ratio of hydrophobic organic matter to total organic matter content;

[0054] S3, performing three-dimensional fluorescence spectrum analysis on each amplified sample and the original reference sample, removing Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample, and using the Raman peak to standardize the three-dimensional fluorescence spectrum data;

[0055] S4, adding the hydrophilic and hydrophobic organic matter data and the three-dimensional fluorescence spectrum data of the reference sample and the amplified sample to the reference database;

[0056] S5, taking an unknown water sample to be tested, measuring its three-dimensional fluorescence spectrum, removing Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample, and using the Raman peak to standardize the three-dimensional fluorescence spectrum data;

[0057] S6, merging the three-dimensional fluorescence spectrum of the sample to be tested with the three-dimensional fluorescence spectrum data of the reference database, decomposing the three-dimensional fluorescence spectrum using the parallel factor method, and constructing the model by setting multiple factor numbers to ensure the stability of the model, so that the residual is minimized and the kernel consistency is maximized, and the split-half test is satisfied;

[0058] S7. According to the parallel factor model, the location of each fluorescent component and the maximum fluorescence intensity of the component are obtained;

[0059] S8. Based on the correlation between the maximum fluorescence intensity of each component and the hydrophilicity and hydrophobicity data of the reference sample, the hydrophilicity and hydrophobicity data of the unknown sample to be tested are obtained.

[0060] The following is a detailed description of the above steps:

[0061] S1: Collection and amplification of reference water samples;

[0062] S101: According to the setting of the water sample points to be tested, a water sample with stable water quality is collected at the same location of the sewage treatment plant as a reference water sample, and is filtered through a 0.45 μm filter membrane for standby use;

[0063] S102: Activate the XAD-8 resin with cyclohexane and methanol, then wash it with ultrapure water, and load 10 mL of the washed XAD-8 resin into the chromatography column;

[0064] S103: continuously injecting the reference water sample into the chromatography column using a peristaltic pump with a flow rate of 3 mL / min;

[0065] S104: Continuously collect the effluent from the chromatography column as amplification samples, the volume of each amplification sample water sample is equal to the volume of the resin, and the samples are numbered consecutively according to the multiple of the resin volume;

[0066] S2: Determine the organic matter content of each amplified sample and the original sample. The hydrophilicity data of all samples are expressed as the ratio of hydrophobic organic matter to total organic matter content. The calculation formula is:

[0067]

[0068] Among them, H i is the hydrophilicity of the i-th sample, C1, C i and C0 are the organic matter concentrations of the first and i-th amplified samples and raw water, respectively; if raw water H is calculated, then C i It is C0;

[0069] Step S3: Figure 2 As shown, each amplified sample and the original reference sample are subjected to three-dimensional fluorescence spectrum analysis, Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample are removed, and the three-dimensional fluorescence spectrum data are standardized using the Raman peak. In this embodiment, the Raman and Rayleigh scattering fluorescence data are subtracted to remove Raman and Rayleigh scattering. In this embodiment, the LS55 fluorescence photometer produced by PerkinElmer of the United States is used to perform three-dimensional fluorescence spectrum analysis on the sample, and the scanning conditions are: the excitation wavelength range is 200-450nm, the emission wavelength range is 250-550nm, the step length of the excitation and emission wavelengths is 5nm, the slit width of the excitation and emission wavelengths is 5nm, and the scanning speed is 1200nm; then, the DOMFluor toolbox in the MATLAB software is used: ① the toolbox is used to subtract blanks and eliminate Rayleigh scattering, ② the Raman peak integral area at the excitation wavelength of 350nm is used for Raman normalization, that is, the standardized value = fluorescence intensity / Raman peak integral area at the excitation wavelength of 350nm.

[0070] S4: Add the hydrophilic and hydrophobic organic matter data and three-dimensional fluorescence spectrum data of the reference sample and the amplified sample to the reference database.

[0071] S5: Figure 3 As shown, an unknown water sample to be tested is taken, its three-dimensional fluorescence spectrum is measured, Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample is removed, and the three-dimensional fluorescence spectrum data is standardized using the Raman peak;

[0072] S6: The three-dimensional fluorescence spectrum of the sample to be tested is combined with the three-dimensional fluorescence spectrum data of the reference database, and the three-dimensional fluorescence spectrum is decomposed by the parallel factor method. To ensure the stability of the model, a model is constructed by setting multiple factor numbers so that the residual is minimized and the kernel consistency is maximized. In this embodiment, the DOM Fluor toolbox in the MATLAB software is used to perform PARAFAC analysis on the three-dimensional fluorescence data of the sample, and the specific steps include:

[0073] S601: merging the reference data and the three-dimensional fluorescence data of the water sample to be tested, and the three-dimensional fluorescence data of i samples form a three-dimensional data matrix of M*N*I;

[0074] S602: Using the trilinear principle of the parallel factor method, the matrix X is decomposed into F factors. Then the original matrix X can be expressed as:

[0075]

[0076] Among them, F represents the number of factors, a m,f represents the vector a f The mth element in a m,f 、b n,f and c i,f Construct matrices A, B, C, x respectively m,n,i (m=1,…,M,n=1,…,N,i=1,…,I) is a three-dimensional data matrix X of M*N*I, e m,n,i (m=1,…,M,n=1,…,N,i=1,…,I) is the three-dimensional error matrix E of M*N*I;

[0077] S603: The three matrices A, B and C decomposed from the matrix X are respectively a score matrix, i.e., a relative mass concentration matrix A of each component, a load matrix B corresponding to the emission spectrum, and a load matrix C corresponding to the excitation spectrum.

[0078] S604: According to formula (2), multiple F values ​​are set, and A is calculated for each F value through loop iteration. T , B T , C T The least squares estimate is performed until E converges to the minimum and the kernel consistency is the highest. At this time, the F value is the optimal value. At this time, the three-dimensional fluorescence data of the sample set can be decomposed into F factors according to the parallel factor method, and the parallel factor model under this time is the optimal model.

[0079] S605: Perform a random split-half test on the established parallel factor model to examine whether the model can pass the split-half test:

[0080] Among them, sample 1 is the sample to be tested during the stable operation of the sewage treatment plant, and it passed the half-split test. Figure 4 As shown;

[0081] Table 1 Ranges of two fluorescent components of the sample to be tested during stable operation of the system

[0082] Components type This study Literature value C1 Protein substances Ex / Em=275 / 330nm Ex / Em=275 / 330 C2 Humic acid Ex / Em=250、285、330 / 425nm Ex / Em=245、335 / 400nm

[0083] Sample 2 is a sample with changed influent quality at the sewage treatment plant. Using the original reference database data, the half-split test failed;

[0084] Sample 2 was used as a new reference sample and amplified using XAD-8 resin;

[0085] The organic matter content of each amplified sample and the original sample was measured, and the hydrophilicity data of all samples were expressed as the ratio of hydrophobic organic matter to total organic matter content;

[0086] Each amplified sample and the original reference sample were subjected to three-dimensional fluorescence spectrum analysis, Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample were removed, and the three-dimensional fluorescence spectrum data were standardized using the Raman peak;

[0087] The three-dimensional fluorescence spectrum was decomposed using the parallel factor method. To ensure the stability of the model, the model was constructed by setting multiple factor numbers to minimize the residual and maximize the kernel consistency, and the split-half test was passed, such as Figure 5 As shown;

[0088] Table 2 Ranges of three fluorescent components of the sample to be tested during the unstable operation of the system

[0089] Components type This study Literature value C1 Protein substances Ex / Em=275 / 330nm Ex / Em=275 / 330 C2 Fulvic Acids Ex / Em=250、285 / 290nm Ex / Em=225,280 / 320nm C3 Humic acid Ex / Em=350 / 435、475nm Ex / Em=335 / 420nm

[0090] The maximum fluorescence intensity F of the components separated by the parallel factor of multiple samples in two cases max It can be seen that humic acid component F max There is little correlation with the hydrophilicity of water samples, while non-humic acid components such as proteins and fulvic acid components F max It has a strong correlation with the hydrophilicity of water samples. Therefore, it is possible to establish the non-humic acid fluorescent component F max Total F max The linear relationship between the ratio of hydrophobic TOC to total TOC is used to use the F of unknown samples to be tested. max The data quickly detects the hydrophilicity and hydrophobicity characteristics of the sample;

[0091] like Figure 6 As shown, non-humic acid fluorescent components F in multiple sewage plant samples max Total F max The correlation between the ratio and the ratio of hydrophobic TOC to total TOC is good, indicating that this method has good universality. Non-humic acid fluorescent component F max Total F max The ratio calculation expression is as follows:

[0092]

[0093] Among them, F max-total F is the component of parallel factor analysis max The sum of max -HA is humic acid component F max value;

[0094] like Figure 7 As shown, after long-term monitoring of the same sampling port of the sewage treatment plant and sufficient supplementation of the reference sample library, this scheme can accurately predict the hydrophilicity information of the dissolved organic matter in the sample.

[0095] The present invention is described in detail above through the embodiments, but the contents are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made according to the scope of application of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from sewage treatment plants based on three-dimensional fluorescence spectroscopy, characterized in that: The method comprises the following steps: S1: Select a stable water sample from the sewage plant to be measured as a reference water sample, and amplify the water sample: S2: Determine the organic matter content of each amplified sample and the original sample. The hydrophilicity data of all samples are expressed as the ratio of hydrophobic organic matter to total organic matter content: S3: Perform three-dimensional fluorescence spectrum analysis on each amplified sample and the original reference sample, remove Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample, and use the Raman peak to standardize the three-dimensional fluorescence spectrum data: S4: Add the hydrophilic and hydrophobic organic matter data and three-dimensional fluorescence spectrum data of the reference sample and the amplified sample to the reference database: S5: Take an unknown water sample to be tested, measure its three-dimensional fluorescence spectrum, remove Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample, and use the Raman peak to standardize the three-dimensional fluorescence spectrum data: S6: The three-dimensional fluorescence spectrum of the sample to be tested is combined with the three-dimensional fluorescence spectrum data of the reference database, and the three-dimensional fluorescence spectrum is decomposed using the parallel factor method. To ensure the stability of the model, the model is constructed by setting multiple factor numbers to minimize the residual and maximize the kernel consistency, and the split-half test is satisfied: S7; According to the parallel factor model, the location of each fluorescent component and the maximum fluorescence intensity of the component are obtained: S8: Based on the linear relationship between the maximum fluorescence intensity of each component and the hydrophilicity data of the reference sample organic matter, the hydrophilicity data of the unknown sample to be tested is obtained.

2. According to claim 1, a method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in sewage plant water samples based on three-dimensional fluorescence spectroscopy, characterized in that: In S1, the water sample amplification is specifically to use XAD-8 resin to adsorb hydrophobic organic components and change the content of organic components in the sample, and the steps include: S101: Collect and select a water sample with stable water quality from the sewage treatment plant to be measured as a reference water sample, and pass the collected water sample through a 0.45 μm filter membrane to remove impurities and suspended matter; S102: Activate the XAD-8 resin with cyclohexane and methanol, then wash it with ultrapure water, and load 10 mL of the washed XAD-8 resin into the chromatography column; S103: using a peristaltic pump to continuously inject the water sample into the chromatography column, the flow rate of the peristaltic pump is 3 mL / min; S104: Continuously collect the effluent from the chromatography column as amplification samples. The volume of each amplification sample is equal to the volume of the resin, and the samples are numbered consecutively according to the multiple of the resin volume.

3. The method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from a sewage treatment plant based on three-dimensional fluorescence spectroscopy according to claim 1, characterized in that: In S2, the method for determining the organic matter content of the amplified sample and the original sample is to determine it by measuring the dissolved organic carbon or chemical oxygen demand of the sample.

4. The method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from a sewage treatment plant based on three-dimensional fluorescence spectroscopy according to claim 3, characterized in that: In the determination method, the hydrophilicity data of all samples are expressed by the ratio of hydrophobic organic matter to total organic matter content, and the calculation formula is: Among them, H i is the hydrophilicity of the i-th sample, C1, C i and C0 are the organic matter concentrations of the first and i-th amplified samples and raw water, respectively; if raw water H is calculated, then C i It's C0.

5. The method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from a sewage treatment plant based on three-dimensional fluorescence spectroscopy according to claim 1, characterized in that: In S3, the Raman and Rayleigh scattering of the three-dimensional fluorescence spectrum of the water sample can be removed by using a subtraction method or an interpolation method.

6. The method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from a sewage treatment plant based on three-dimensional fluorescence spectroscopy according to claim 5, characterized in that: The subtraction method is to directly delete the Raman or Rayleigh scattering fluorescence data, and the interpolation method is to fit the normal fluorescence signal intensity on both sides of the Rayleigh scattering band using the cubic spline interpolation method to eliminate the abnormal fluorescence value caused by Rayleigh scattering; the three-dimensional fluorescence data standardization is to standardize each fluorescence data of the three-dimensional fluorescence spectrum by the integral area of ​​the pure water Raman peak at the excitation wavelength of 350nm.

7. The method for rapidly analyzing the hydrophilicity and hydrophobicity of dissolved organic matter in water samples from a sewage treatment plant based on three-dimensional fluorescence spectroscopy according to claim 1, characterized in that: S6 specifically includes the following steps: S601: merging the reference data and the three-dimensional fluorescence data of the water sample to be tested, and forming the three-dimensional fluorescence data of i samples into a three-dimensional data matrix of M*N*I; S602: Using the trilinear principle of the parallel factor method, the matrix X is decomposed into F factors. Then the original matrix X can be expressed as: Among them, F represents the number of factors, a m,f represents the vector a f The mth element in a m,f 、b n,f and c i,f Construct matrices A, B, C, x respectively m,n,i (m=1,…,M,n=1,…,N,i=1,…,I) is a three-dimensional data matrix X of M*N*I, e m,n,i (m=1,…,M,n=1,…,N,i=1,…,I) is the three-dimensional error matrix E of M*N*I; S603: The three matrices A, B and C decomposed from the matrix X are respectively a score matrix, i.e., a relative mass concentration matrix A of each component, a load matrix B corresponding to the emission spectrum, and a load matrix C corresponding to the excitation spectrum. S604: According to formula (2), multiple F values ​​are set, and A is calculated for each F value through loop iteration. T , B T , C T The least squares estimate is performed until E converges to the minimum and the kernel consistency is the highest. At this time, the F value is the optimal value. At this time, the three-dimensional fluorescence data of the sample set can be decomposed into F factors according to the parallel factor method, and the parallel factor model under this time is the optimal model. S605: Perform a random split-half test on the established parallel factor model to examine whether the model can pass the split-half test: If the established parallel factor model satisfies the split-half test, proceed to the subsequent process; If the established parallel factor model does not satisfy the split-half test, the sample to be tested is used as a new reference sample, sample amplification is performed, and the organic matter concentration and three-dimensional fluorescence spectrum are analyzed and included in the reference database, that is, the sample to be tested repeats steps S1 to S4.

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