CN113484294A - Diagnosis method for binding capacity of soluble organic carbon and different valence layer electronic configuration metal - Google Patents

Diagnosis method for binding capacity of soluble organic carbon and different valence layer electronic configuration metal Download PDF

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CN113484294A
CN113484294A CN202110848746.8A CN202110848746A CN113484294A CN 113484294 A CN113484294 A CN 113484294A CN 202110848746 A CN202110848746 A CN 202110848746A CN 113484294 A CN113484294 A CN 113484294A
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蒲晓
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Abstract

The invention relates to a method for diagnosing the binding capacity of soluble organic carbon and different valence layer electronic configuration metals, belonging to the technical field of water ecology. Firstly, obtaining soluble organic carbon (DOC) components with different molecular weights by an ultrafiltration fractionation technology, wherein the soluble organic carbon (DOC) components comprise 0.1-1 kDa, 1-5 kDa, 5-10 kDa and 10-100 kDa DOC; then, carrying out fluorescence quenching titration experiments on DOCs with different molecular weights and metal ions with different valence layer electronic configurations (p, d and s areas) on the periodic table of elements respectively; after the experiment is finished, three-dimensional fluorescence spectra of DOCs with different molecular weights before and after the titration experiment are determined, and fluorescence components participating in combination and fluorescence quenching curves of the components are obtained through parallel factor analysis (PARAFAC); and finally, calculating by using a modified Stren-Volmer model to obtain the binding parameters of different fluorescent components and the electronic configuration metals of different valence layers, and obtaining the affinity difference of the binding of the different components and the metals.

Description

Diagnosis method for binding capacity of soluble organic carbon and different valence layer electronic configuration metal
Technical Field
The invention relates to the technical field of water ecology, in particular to a method for diagnosing the binding capacity of soluble organic carbon and different valence layer electronic configuration metals.
Background
The soluble organic carbon (DOC) is an important water chemical index representing the level of water soluble organic substances, is a very active chemical substance in a water body ring, and has the characteristics of wide molecular weight range, complex composition and the like; DOC is an important carbon source for planktonic bacteria reproduction and metabolism, reflects the water environment pollution condition in a water body, also represents the influence of human activities such as fertilization and irrigation, industrial construction, vegetation destruction and the like on water quality, utilizes the effectiveness of the water body quality to be reflected to different degrees, and further achieves the purpose of effectively monitoring the organic carbon content and the water quality of the water body through detection, and simultaneously, the DOC can interact with metal ions to form an organic metal complex, so that the toxicity and bioavailability of free metal ions to aquatic organisms can be reduced, but the binding capacities of metals with different valence layer electronic configurations and the DOC are different; metals are widely existed in water environment, and the metals in sediments or surrounding soil can also enter a water body through release and runoff, so that the water body has metal pollution risk; in metals with different valence layer electronic configuration on the periodic table of elements (including s, p and d regions), most metals in the p region and the d region have toxic effects on human health, and once the concentration of the metals in the water environment exceeds a threshold value, the toxic effects become obvious and can be enriched in organisms through migration transformation or physicochemical effects to aggravate ecological risks caused to the water environment.
Because metal ions can interact with substances in the surrounding environment and are influenced by various environmental factors, the pollution caused by metal and the possibly caused ecological risk need to be judged according to the environment where the metal is located, wherein DOC is one of the main influencing factors influencing the metal environmental risk; the metal ions can interact with the DOC to form an organic metal complex, and the organic metal complex becomes a means for monitoring and measuring water quality, but the binding capacity of metals with different valence layer electronic configurations (including s, p and d zones) and the DOC is different compared with the s zone (Ca zone)2+、Mg2+、Na+) Metallic element, p-region (Al)3+、Pb2+) And d zone (Cd)2+、Cu2+、Fe3+、Fe2+、Zn2+) The coordination capacity of the metal elements is higher, and meanwhile, the pollution and the biological toxicity are stronger, so that the important distinction is needed; for example, the invention discloses a method for estimating the concentration of dissolved organic carbon in lakes, which is disclosed by the Chinese patent No. CN201811072505.3, constructs the correlation between the actually measured salinity S and DOC concentration in lakes by a data fitting analysis method and using the actually measured data, and measures the concentrations in the fieldAfter the salinity value of the water body is determined, the DOC concentration of the surface water body is timely, quickly and accurately estimated; however, with the difference of lake distribution and different offshore and inland environments, the metal ions contained in the soil are greatly different, the DOC concentration also changes due to the interaction between non-salt substances in the surrounding environment, so the measurement range cannot be limited to only the correlation between salinity and DOC, and the s region (Ca region) is also different because the binding capacity of metals with different valence layer electronic configurations and DOC is different2+、Mg2+、Na+) DOC combined by metal elements has far less environmental pollution than p-zone (Al)3+、Pb2+) And d zone (Cd)2+、Cu2+、Fe3+、Fe2+、Zn2+) Pollution caused by metal elements is insufficient to accurately estimate the surface water body DOC concentration only by means of salinity measurement, and the DOC concentration obtained by not subdividing electronic configuration metals of different valence layers cannot be used as a discrimination standard of water body quality; therefore, the intensive study on the binding capacity of the DOC and metals with different valence layer electronic configuration, especially toxic and harmful heavy metals in p and d regions provides valuable information and reliable basis for evaluating and predicting the environmental behaviors of different metals in different water bodies.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the diagnosis method for the binding capacity of the soluble organic carbon and the electronic configuration metals of different valence layers is provided aiming at the problem that the binding capacity of the electronic configuration metals of different valence layers, particularly the toxic and harmful heavy metals in p and d regions is different from that of DOC, and the environmental behaviors of different metals in different water bodies cannot be effectively estimated. According to the diagnosis method provided by the invention, the binding capacity of the DOC and metals with different valence layer electronic configurations, especially the toxic and harmful heavy metals in p and d regions can be deeply researched, and valuable information and reliable basis can be provided for evaluating and predicting the environmental behaviors of different metals in different water bodies.
In order to solve the technical problems, the invention adopts the technical scheme that:
a diagnostic method for the binding capacity of soluble organic carbon and different valence layer electronic configuration metals is characterized by comprising the following specific process steps:
(1) water sample pretreatment:
according to the principle of parallel factor analysis, 20-40 sampling sections are arranged in a research area, the sampling sections are collected at a position about 0.5 m below the water surface of each sampling section, a sampling bottle is pre-washed for 3 times by using a water sample before sampling, 3 parts of parallel water samples are collected on each section and then mixed to obtain a sample, the sample is taken back to a laboratory for filtering by using a 0.45-micron glass fiber filter membrane and a vacuum filter, and then the sample is refrigerated and stored in a dark place at 4 ℃ to prepare a pre-treated water sample;
(2) DOC molecular weight fractionation:
performing DOC molecular weight classification on the filtered pretreated water sample by using an ultrafiltration method, wherein the used instruments are an ultrafiltration cup and an ultrafiltration membrane, before the start of an experiment, respectively using a NaOH solution with the mass fraction of 50-60% and an HCl solution with the mass fraction of 60-70% to stir and clean the ultrafiltration membrane without pressurization, then adding deionized water to pressurize and stir and clean the ultrafiltration membrane, firstly performing ultrafiltration on 100 mL of ultrapure water before formal ultrafiltration, after the ultrafiltration is completed, taking a 10kDa ultrafiltration membrane at 25 ℃ for later use, putting 200 mL of the pretreated water sample into the ultrafiltration cup to pass through the membrane in a pressurized manner, pressurizing by using nitrogen, collecting filtrate under the membrane, adding 10 mL of deionized water into the ultrafiltration cup when 50 mL of the pretreated water sample remains, then continuously performing pressure stirring and filtration to obtain 10 mL, then adding 10 mL of deionized water into the ultrafiltration cup, performing pressure stirring and filtration to obtain 10 mL, then pouring out the concentrated solution on the membrane and adding 150 mL of deionized water into the ultrafiltration cup, namely, the DOC solution is 10-100 kDa, 30 mL of deionized water is added into the filtrate under the membrane to be regarded as 0.1-10 kDa DOC solution, the DOC solution is sequentially passed through the membrane according to the method, the sequence is 10kDa → 5 kDa → 1kDa, and finally four molecular weight segments of DOC are obtained: 0.1-1 kDa, 1-5 kDa, 5-10 kDa and 10-100 kDa to prepare four DOC sample solutions;
(3) fluorescence quenching titration experiment:
adding deionized water into the four DOC sample solutions for dilution until the concentration of all the DOC sample solutions is 1-10 mg.L-1In the range of (1), 30 mL of each DOC sample solution was taken and put into a conical flask, and 0.01 mol. L. of 0, 60, 120, 180, 240, 300. mu.L of each DOC sample solution was added dropwise into the conical flask-1OfThe metal solution with the electronic configuration of the valence layer ensures that the metal ion concentration in the conical flask is respectively 0, 20, 40, 60, 80 and 100 mu mol.L-1Neglecting the concentration dilution effect, placing all samples in a constant-temperature oscillation box to avoid light and oscillate for 24 hours after titration to prepare an experimental solution;
(4) three-dimensional fluorescence spectrum scanning:
taking out the combined and balanced experimental solution, and setting the excitation wavelength and the emission wavelength ranges to be 220-450 nm and 290-600 nm respectively through three-dimensional fluorescence spectrum scanning to obtain three-dimensional fluorescence scanning data of all samples;
(5) parallel factor analysis:
performing parallel factor analysis on the three-dimensional fluorescence spectrum scanning data of all experimental solutions to obtain the maximum fluorescence intensity of different fluorescence components in each water sample;
(6) calculation of binding parameters:
the modified Stren-Volmer model is adopted to determine the binding parameters between the metal and the parallel factor analysis derived fluorescent component, and the calculation formula is as follows:
fitting a modified Stren-Volmer model: f0/（F0-F）=1/（f*K*CM）+1/f（1）。
The pore diameters of the ultrafiltration membrane in the step (2) are respectively 10kDa, 5 kDa and 1 kDa.
The metal solution in the step (3) is Cu2+、Pb2+And (3) solution.
The three-dimensional fluorescence spectrum scanning in the step (4) comprises the following specific steps:
(1) three-dimensional fluorescence spectrum scanning is carried out on the fluorescence spectrum analyzer, and the instrument is equipped with 1 cm quartz cuvette, adopts 150W xenon arc lamp as excitation light source, PMT voltage = 400V, and signal-to-noise ratio 110 ~ 220, response time are set as automatic, scanning speed: 60000 nm · min-1The excitation wavelength range lambda EX = 220-450 nm, the interval is 5 nm, the emission wavelength range lambda Em = 290-600 nm, the interval is 1 nm, and the scanning spectrum is used for automatic instrument correction;
(2) two-dimensional scanning and three-dimensional scanning are carried out by ultrapure water before the fluorescence of the experimental solution is measured, so as to carry out Raman scattering correction and contrast of fluorescence spectrum on the measurement result, wherein the unit of fluorescence intensity is R.U.
The specific steps of the parallel factor analysis in the step (5) are as follows:
(1) obtaining common fluorescent components of multiple DOCs by parallel factor analysis, carrying out parallel factor analysis on the processed fluorescent data set through MATLAB R2016a software, and determining the quantity of the fluorescent components through methods such as residual analysis, core consistency analysis and half-test;
(2) the obtained maximum fluorescence intensity of each fluorescent component can be compared with the quenching intensity of metal ions with different valence layer electronic configurations to different fluorescent components of DOC by comparing the maximum fluorescence intensities.
The modified Stren-Volmer model in the step (6) comprises:
F0is the fluorescence intensity at the start of titration, i.e., when no metal is added, and F is the metal concentration CMmol·L-1The fluorescence intensity of (b).
The modified Stren-Volmer model in the step (6) comprises:
and (3) taking logarithm of the conditional stability constant K and the ratio f of the fluorescent group participating in metal ion coordination to obtain a binding stability constant lgK.
The numerical relationship in the modified Stren-Volmer model in the step (6) is as follows:
(1) calculating the ratio f of the fluorescent groups participating in the coordination of the metal ions through 1/f;
(2) the conditional stability constant K was calculated by 1/f x K and logarithmized to give the binding stability constant lgK.
The lgK value may characterize the difference in binding ability of metal ions of different valence layer electronic configurations to the DOC.
The invention has the beneficial effects that:
(1) firstly, subdividing soluble organic carbon (DOC) components by an ultrafiltration fractionation technology to obtain DOC components with different molecular weights, wherein the DOC components comprise four DOC sample solutions of 0.1-1 kDa, 1-5 kDa, 5-10 kDa and 10-100 kDa DOC, so as to obtain more experimental control cases and widen the coverage range of the experimentThe method improves the scientificity and reliability of the diagnosis method, carries out fluorescence quenching titration experiments on DOC sample solutions with different molecular weights and metal ions with different valence layer electronic configurations (p, d and s areas) on the periodic table of elements respectively, and deeply researches the DOC and the metals with the different valence layer electronic configurations, especially heavy metal Cu with high toxicity with the p and d areas by utilizing the subdivision of the metal valence layer electronic configurations2+、Pb2+The binding capacity of the two groups of the three groups of the four groups; according to the invention, DOC samples with different molecular weights after grading are diluted to be consistent, so that the influence of DOC concentration and internal filtering effect are reduced as much as possible, and the rationality and accuracy of the diagnosis method are further improved;
(2) the invention measures the three-dimensional fluorescence spectra of DOC sample solutions with different molecular weights before and after titration experiment, and adds Cu2+All DOC samples of (1) and addition of Pb2+All DOC samples are subjected to parallel factor analysis respectively, fluorescent components participating in combination and fluorescence quenching curves of the components are obtained through the parallel factor analysis, two fluorescent components are mainly identified, namely a humoid substance C1 and a proteinoid substance C2, the metal ion and DOC combining capacity is accurately determined by utilizing the adsorption and ion exchange effects of organic colloid contained in the humoid substance on metal ions and the integration and complexation effects of humic acid in humic substances on elements, and the metal ions mainly react with the humoid substance in a combined manner, so that the accuracy and the scientificity of the diagnosis method are ensured by detecting the metal ions; a small part of fixed metal can also react with protein substances, the fixed metal and protein can generate chelation under the control of mainly electrostatic action and secondarily coordination action to further adsorb, and the DOC and metals with different valence layer electronic configuration can be more comprehensively measured by parallel factor analysis, so that the diagnosis method is more comprehensive and scientific, the influence of environmental factors is reduced as much as possible by analyzing the interaction of metal ions and substances in the surrounding environment, the undetermined metal ions are reduced, and the accuracy of the diagnosis method is improved; the invention utilizes a modified Stren-Volmer model to calculate and obtain the combination parameters of different fluorescent components and different valence layer electronic configuration metalsThe method accurately obtains the affinity difference of the combination of different components and metals, and has wide application prospect.
Drawings
FIG. 1 illustrates the identification of two fluorescent components of different molecular weight DOC by PARAFAC;
FIG. 2 shows the dropwise addition of Cu2+And Pb2+Fmax change for post fluorescent components C1, C2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a diagnostic method for the binding capacity of soluble organic carbon and different valence layer electronic configuration metals is characterized by comprising the following specific process steps:
(1) water sample pretreatment:
according to the principle of parallel factor analysis, 20 sampling sections are arranged in a research area, the sampling sections are collected at the position about 0.5 m below the water surface of each sampling section, a sampling bottle is pre-washed for 3 times by using a water sample before sampling, 3 parts of parallel water samples are collected on each section and then mixed to obtain a sample, the sample is taken back to a laboratory for filtering by using a 0.45-micrometer glass fiber filter membrane and a vacuum filter, and then the sample is refrigerated and stored in a dark place at 4 ℃ to prepare a pretreated water sample.
(2) DOC molecular weight fractionation:
performing DOC molecular weight classification on the filtered pretreated water sample by using an ultrafiltration method, wherein the used instruments are an ultrafiltration cup and an ultrafiltration membrane, before the start of an experiment, respectively using a NaOH solution with the mass fraction of 50% and an HCl solution with the mass fraction of 60% to stir and clean the ultrafiltration membrane without pressurization, then adding deionized water to pressurize and stir and clean the ultrafiltration membrane, firstly performing ultrafiltration on 100 mL of ultrapure water before formal ultrafiltration, after the ultrafiltration is completed, taking a 10kDa ultrafiltration membrane for later use under the condition of 25 ℃, putting 200 mL of the pretreated water sample into the ultrafiltration cup to perform membrane pressurization and filtration, using nitrogen to perform pressurization, collecting filtrate under the membrane, adding 10 mL of deionized water into the ultrafiltration cup when the rest 50 mL of the pretreated water sample is left, then continuing to perform pressurization and stirring and filtration to obtain 10 mL, then adding 10 mL of deionized water into the ultrafiltration cup, performing pressurization and stirring and filtration to obtain 10 mL, then pouring out a concentrated solution on the membrane and adding 150 mL of deionized water, namely, the DOC solution is 10-100 kDa, 30 mL of deionized water is added into the filtrate under the membrane to be regarded as 0.1-10 kDa DOC solution, the DOC solution is sequentially passed through the membrane according to the method, the sequence is 10kDa → 5 kDa → 1kDa, and finally four molecular weight segments of DOC are obtained: 0.1-1 kDa, 1-5 kDa, 5-10 kDa and 10-100 kDa to prepare four DOC sample solutions.
(3) Fluorescence quenching titration experiment:
adding deionized water into the four DOC sample solutions for dilution until the concentration of all the DOC sample solutions is 1 mg.L-1In the range of (1), 30 mL of each DOC sample solution was taken and put into a conical flask, and 0.01 mol. L. of 0, 60, 120, 180, 240, 300. mu.L of each DOC sample solution was added dropwise into the conical flask-1The metal solution with different valence layer electronic configuration in the conical flask is respectively provided with metal ion concentrations of 0, 20, 40, 60, 80 and 100 mu mol.L-1Neglecting the concentration dilution effect, placing all samples in a constant-temperature oscillation box to avoid light and oscillate for 24 hours after titration to prepare an experimental solution;
(4) three-dimensional fluorescence spectrum scanning:
taking out the combined and balanced experimental solution, and setting the excitation wavelength and the emission wavelength ranges to be 220nm and 290nm respectively through three-dimensional fluorescence spectrum scanning to obtain three-dimensional fluorescence scanning data of all samples;
(5) parallel factor analysis:
performing parallel factor analysis on the three-dimensional fluorescence spectrum scanning data of all experimental solutions to obtain the maximum fluorescence intensity of different fluorescence components in each water sample;
(6) calculation of binding parameters:
the modified Stren-Volmer model is adopted to determine the binding parameters between the metal and the parallel factor analysis derived fluorescent component, and the calculation formula is as follows:
fitting a modified Stren-Volmer model: f0/（F0-F）=1/（f*K*CM）+1/f（1）。
The pore diameters of the ultrafiltration membrane in the step (2) are respectively 10kDa, 5 kDa and 1 kDa.
The metal solution in the step (3) is Cu2+、Pb2+And (3) solution.
The three-dimensional fluorescence spectrum scanning in the step (4) comprises the following specific steps:
(1) three-dimensional fluorescence spectrum scanning is carried out on the fluorescence spectrum analyzer, and the instrument is equipped with 1 cm quartz cuvette, adopts 150W xenon arc lamp as excitation light source, PMT voltage = 400V, and SNR 110, response time set to automatic, scanning speed: 60000 nm · min-1The excitation wavelength range lambda EX =220nm, the interval is 5 nm, the emission wavelength range lambda Em =290nm, the interval is 1 nm, and the scanning spectrum is used for automatic instrument correction;
(2) two-dimensional scanning and three-dimensional scanning are carried out by ultrapure water before the fluorescence of the experimental solution is measured, so as to carry out Raman scattering correction and contrast of fluorescence spectrum on the measurement result, wherein the unit of fluorescence intensity is R.U.
The specific steps of the parallel factor analysis in the step (5) are as follows:
(1) obtaining common fluorescent components of multiple DOCs by parallel factor analysis, carrying out parallel factor analysis on the processed fluorescent data set through MATLAB R2016a software, and determining the quantity of the fluorescent components through methods such as residual analysis, core consistency analysis and half-test;
(2) the obtained maximum fluorescence intensity of each fluorescent component can be compared with the quenching intensity of metal ions with different valence layer electronic configurations to different fluorescent components of DOC by comparing the maximum fluorescence intensities.
Example 2:
a diagnostic method for the binding capacity of soluble organic carbon and different valence layer electronic configuration metals is characterized by comprising the following specific process steps:
(1) water sample pretreatment:
according to the principle of parallel factor analysis, 30 sampling sections are arranged in a research area, the sampling sections are collected at a position about 0.5 m below the water surface of each sampling section, a sampling bottle is pre-washed for 3 times by using a water sample before sampling, 3 parts of parallel water samples are collected and mixed at each section to obtain a sample, the sample is taken back to a laboratory for filtering by using a 0.45-micrometer glass fiber filter membrane and a vacuum filter, and then the sample is refrigerated and stored in a dark place at 4 ℃ to prepare a pretreated water sample;
(2) DOC molecular weight fractionation:
performing DOC molecular weight classification on the filtered pretreated water sample by using an ultrafiltration method, wherein the used instruments are an ultrafiltration cup and an ultrafiltration membrane, before the start of an experiment, respectively using 55 mass percent NaOH solution and 65 mass percent HCl solution to stir and clean the ultrafiltration membrane without pressurization, then adding deionized water to pressurize and stir and clean the ultrafiltration membrane, firstly performing ultrafiltration on 100 mL of ultrapure water before formal ultrafiltration, after the ultrafiltration is completed, taking a 10kDa ultrafiltration membrane for standby at 25 ℃, putting 200 mL of the pretreated water sample into the ultrafiltration cup to pass through the membrane under pressurization by using nitrogen, collecting filtrate under the membrane, adding 10 mL of deionized water into the ultrafiltration cup when the residual 50 mL of the pretreated water sample is left, then continuing to perform pressure stirring and filtration to obtain 10 mL, then adding 10 mL of deionized water into the ultrafiltration cup, performing pressure stirring and filtration to obtain 10 mL, then pouring out the concentrated solution on the membrane and adding 150 mL of deionized water, namely, the DOC solution is 10-100 kDa, 30 mL of deionized water is added into the filtrate under the membrane to be regarded as 0.1-10 kDa DOC solution, the DOC solution is sequentially passed through the membrane according to the method, the sequence is 10kDa → 5 kDa → 1kDa, and finally four molecular weight segments of DOC are obtained: 0.1-1 kDa, 1-5 kDa, 5-10 kDa and 10-100 kDa to prepare four DOC sample solutions;
(3) fluorescence quenching titration experiment:
adding deionized water into the four DOC sample solutions for dilution until the concentration of all the DOC sample solutions is 5 mg.L-1In the range of (1), 30 mL of each DOC sample solution was taken and put into a conical flask, and 0.01 mol. L. of 0, 60, 120, 180, 240, 300. mu.L of each DOC sample solution was added dropwise into the conical flask-1The metal solution with different valence layer electronic configuration in the conical flask is respectively provided with metal ion concentrations of 0, 20, 40, 60, 80 and 100 mu mol.L-1Neglecting the concentration dilution effect, placing all samples in a constant-temperature oscillation box to avoid light and oscillate for 24 hours after titration to prepare an experimental solution;
(4) three-dimensional fluorescence spectrum scanning:
taking out the combined and balanced experimental solution, and setting the excitation wavelength and the emission wavelength ranges to be 300nm and 450nm respectively through three-dimensional fluorescence spectrum scanning to obtain three-dimensional fluorescence scanning data of all samples;
(5) parallel factor analysis:
performing parallel factor analysis on the three-dimensional fluorescence spectrum scanning data of all experimental solutions to obtain the maximum fluorescence intensity of different fluorescence components in each water sample;
(6) calculation of binding parameters:
the modified Stren-Volmer model is adopted to determine the binding parameters between the metal and the parallel factor analysis derived fluorescent component, and the calculation formula is as follows:
fitting a modified Stren-Volmer model: f0/（F0-F）=1/（f*K*CM）+1/f（1）。
The pore diameters of the ultrafiltration membrane in the step (2) are respectively 10kDa, 5 kDa and 1 kDa.
The metal solution in the step (3) is Cu2+And (3) solution.
The three-dimensional fluorescence spectrum scanning in the step (4) comprises the following specific steps:
(1) three-dimensional fluorescence spectrum scanning is carried out on the fluorescence spectrum analyzer, and the instrument is equipped with 1 cm quartz cuvette, adopts 150W xenon arc lamp as excitation light source, PMT voltage = 400V, and SNR 150, response time are set as automatic, scanning speed: 60000 nm · min-1The excitation wavelength range lambda EX =300nm, the interval is 5 nm, the emission wavelength range lambda Em =400nm, the interval is 1 nm, and the scanning spectrum is used for automatic instrument correction;
(2) two-dimensional scanning and three-dimensional scanning are carried out by ultrapure water before the fluorescence of the experimental solution is measured, so as to carry out Raman scattering correction and contrast of fluorescence spectrum on the measurement result, wherein the unit of fluorescence intensity is R.U.
The specific steps of the parallel factor analysis in the step (5) are as follows:
(1) obtaining common fluorescent components of multiple DOCs by parallel factor analysis, carrying out parallel factor analysis on the processed fluorescent data set through MATLAB R2016a software, and determining the quantity of the fluorescent components through methods such as residual analysis, core consistency analysis and half-test;
(2) the obtained maximum fluorescence intensity of each fluorescent component can be compared with the quenching intensity of metal ions with different valence layer electronic configurations to different fluorescent components of DOC by comparing the maximum fluorescence intensities.
Example 3:
a diagnostic method for the binding capacity of soluble organic carbon and different valence layer electronic configuration metals is characterized by comprising the following specific process steps:
(1) water sample pretreatment:
according to the principle of parallel factor analysis, 40 sampling sections are arranged in a research area, the sampling sections are collected at a position about 0.5 m below the water surface of each sampling section, a sampling bottle is pre-washed for 3 times by using a water sample before sampling, 3 parts of parallel water samples are collected and mixed at each section to obtain a sample, the sample is taken back to a laboratory for filtering by using a 0.45-micron glass fiber filter membrane and a vacuum filter, and then the sample is refrigerated and stored in a dark place at 4 ℃ to prepare a pretreated water sample;
(2) DOC molecular weight fractionation:
performing DOC molecular weight classification on the filtered pretreated water sample by using an ultrafiltration method, wherein the used instruments are an ultrafiltration cup and an ultrafiltration membrane, before the start of an experiment, respectively using 55 mass percent NaOH solution and 70 mass percent HCl solution to stir and clean the ultrafiltration membrane without pressurization, then adding deionized water to pressurize and stir and clean the ultrafiltration membrane, firstly performing ultrafiltration on 100 mL of ultrapure water before formal ultrafiltration, after the ultrafiltration is completed, taking a 10kDa ultrafiltration membrane for standby at 25 ℃, putting 200 mL of the pretreated water sample into the ultrafiltration cup to pass through the membrane under pressurization by using nitrogen, collecting filtrate under the membrane, adding 10 mL of deionized water into the ultrafiltration cup when the residual 50 mL of the pretreated water sample is left, then continuing to perform pressure stirring and filtration to obtain 10 mL, then adding 10 mL of deionized water into the ultrafiltration cup, performing pressure stirring and filtration to obtain 10 mL, then pouring out the concentrated solution on the membrane and adding 150 mL of deionized water, namely, the DOC solution is 10-100 kDa, 30 mL of deionized water is added into the filtrate under the membrane to be regarded as 0.1-10 kDa DOC solution, the DOC solution is sequentially passed through the membrane according to the method, the sequence is 10kDa → 5 kDa → 1kDa, and finally four molecular weight segments of DOC are obtained: 0.1-1 kDa, 1-5 kDa, 5-10 kDa and 10-100 kDa to prepare four DOC sample solutions;
(3) fluorescence quenching titration experiment:
adding deionized water into the four DOC sample solutions for dilution until the concentration of all the DOC sample solutions is 10 mg.L-1In the range of (1), 30 mL of each DOC sample solution was taken and put into a conical flask, and 0.01 mol. L. of 0, 60, 120, 180, 240, 300. mu.L of each DOC sample solution was added dropwise into the conical flask-1The metal solution with different valence layer electronic configuration in the conical flask is respectively provided with metal ion concentrations of 0, 20, 40, 60, 80 and 100 mu mol.L-1Neglecting the concentration dilution effect, placing all samples in a constant-temperature oscillation box to avoid light and oscillate for 24 hours after titration to prepare an experimental solution;
(4) three-dimensional fluorescence spectrum scanning:
taking out the combined and balanced experimental solution, and setting the excitation wavelength and the emission wavelength ranges to be 450nm and 600nm respectively through three-dimensional fluorescence spectrum scanning to obtain three-dimensional fluorescence scanning data of all samples;
(5) parallel factor analysis:
performing parallel factor analysis on the three-dimensional fluorescence spectrum scanning data of all experimental solutions to obtain the maximum fluorescence intensity of different fluorescence components in each water sample;
(6) calculation of binding parameters:
the modified Stren-Volmer model is adopted to determine the binding parameters between the metal and the parallel factor analysis derived fluorescent component, and the calculation formula is as follows:
fitting a modified Stren-Volmer model: f0/（F0-F）=1/（f*K*CM）+1/f（1）。
The pore diameters of the ultrafiltration membrane in the step (2) are respectively 10kDa, 5 kDa and 1 kDa.
The metal solution in the step (3) is Pb2+And (3) solution.
The three-dimensional fluorescence spectrum scanning in the step (4) comprises the following specific steps:
(1) three-dimensional fluorescence spectrum scanning is carried out on a fluorescence spectrum analyzer which is matched with a 1 cm stoneThe quartz cuvette, the 150W xenon arc lamp as the excitation light source, PMT voltage = 400V, signal-to-noise ratio 220, response time set as automatic, scanning speed: 60000 nm · min-1The excitation wavelength range lambda EX =450 nm, the interval is 5 nm, the emission wavelength range lambda Em =600nm, the interval is 1 nm, and the scanning spectrum is used for automatic instrument correction;
(2) two-dimensional scanning and three-dimensional scanning are carried out by ultrapure water before the fluorescence of the experimental solution is measured, so as to carry out Raman scattering correction and contrast of fluorescence spectrum on the measurement result, wherein the unit of fluorescence intensity is R.U.
The specific steps of the parallel factor analysis in the step (5) are as follows:
(1) obtaining common fluorescent components of multiple DOCs by parallel factor analysis, carrying out parallel factor analysis on the processed fluorescent data set through MATLAB R2016a software, and determining the quantity of the fluorescent components through methods such as residual analysis, core consistency analysis and half-test;
(2) the obtained maximum fluorescence intensity of each fluorescent component can be compared with the quenching intensity of metal ions with different valence layer electronic configurations to different fluorescent components of DOC by comparing the maximum fluorescence intensities.
The detection method comprises the following steps:
DOC is selected from DOC of park landscape water body, d region and p region are selected from electronic configurations of different valence layers, and corresponding metal ions are Cu respectively2+And Pb2+。
(1) Fluorescent components identified in the combined water sample
After the titration experiment is finished, Cu is added2+All DOC samples of (1) and addition of Pb2+All DOC-like samples were subjected to parallel factor analysis, respectively, and two fluorescent components were identified (fig. 1), humoid substance C1 (Ex/Em =245(270)/436 nm) and proteoid substance C2 (Ex/Em =225(285)/347 nm), respectively. Table 1 lists the types and wavelength ranges of the two fluorescent components and their comparison with previous findings.
The results of the fluorescent component showed that Cu is used2+And Pb2+The d-block and p-block metals, when combined with a DOC, are identical in fluorescent components that participate in the combination and are not charged with layers of different valenciesThe sub-configuration is changed.
(2) Judgment of combining capacity of different valence layer electronic configuration metals and DOC
a. Determination of binding Capacity Difference by comparison of fluorescence quenching degrees of fluorescent Components
Cu2+、Pb2+The reaction with the components C1 and C2 shows fluorescence quenching effect. Wherein Cu2+The quenching effect on two fluorescent components in DOC with any molecular weight section is stronger than that of Pb2+。
The degree of quenching of the fluorescent component indicates that Cu is used2+And Pb2+The represented d-zone metal and p-zone metal are combined with two fluorescent components in the park landscape water body and cause DOC fluorescence to be quenched, but the d-zone metal (Cu)2+) Quenching degrees stronger than p-region metal (Pb) for two fluorescent components in DOC2+) The result shows that the binding capacity of the d-zone metal and two fluorescent components in the DOC of the park landscape water body is stronger than that of the p-zone metal.
The difference of the binding capacity is judged by comparing the binding parameters of the fluorescent component and the electronic configuration metal of different valence layers
Two fluorescent components and Cu in DOC with different molecular weights2+All of the binding stability constants of (a) are greater than Pb2+And the complex stability constant of both heavy metals is the largest when the heavy metals are complexed with DOC with the molecular weight of less than 1 kDa. The result shows that Cu is used in the process of combining with DOC (DOC) of park landscape water body2+The binding capacity of the represented d-block metal and the two fluorescent components is stronger than that of Pb2+Representative p-region metals. Meanwhile, the difference of the binding capacity of the metals with different valence layer electronic configurations and the DOC is not influenced by the DOC molecular weight, namely no matter what molecular weight section, the binding capacity of the d-area metal and the DOC is stronger than that of the p-area metal.
TABLE 1 location of fluorescent component and comparison thereof with previous studies
Figure DEST_PATH_IMAGE001
TABLE 2 DOC in combination with different valence layer electronic configuration metalslgK、f、R2Value of
Figure 872433DEST_PATH_IMAGE002
In the above experiment, in example 2 and example 3, only one metal ion is selected for the electronic configurations (p region and d region) of different valence layers, and research results show that when the two metals with the electronic configurations of different valence layers are combined with the DOC, the combined components are the same, but the combining capacity with different components is different, wherein the combining capacity of the d region metal to the two fluorescent components in the DOC is stronger than that of the p region metal; example 1 using a two-metal ion mixing test, when combined with a park landscape water body DOC, the components that are combined are the same but the combining ability of different components is consistent with examples 2 and 3, namely, the difference of the combining ability of the electronic configuration metal of different valence layers and the DOC is not influenced by the molecular weight of the DOC, and the fact that the combining ability of the d-block metal and the DOC is stronger than that of the p-block metal in any molecular weight section is also demonstrated.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference thereto is therefore intended to be embraced therein.

Claims (9)

1. A diagnostic method for the binding capacity of soluble organic carbon and different valence layer electronic configuration metals is characterized by comprising the following specific steps:
(1) water sample pretreatment:
according to the principle of parallel factor analysis, 20-40 sampling sections are arranged in a research area, the sampling sections are collected at a position about 0.5 m below the water surface of each sampling section, a sampling bottle is pre-washed for 3 times by using a water sample before sampling, 3 parts of parallel water samples are collected on each section and then mixed to obtain a sample, the sample is taken back to a laboratory for filtering by using a 0.45-micron glass fiber filter membrane and a vacuum filter, and then the sample is refrigerated and stored in a dark place at 4 ℃ to prepare a pre-treated water sample;
(2) DOC molecular weight fractionation:
performing DOC molecular weight classification on the filtered pretreated water sample by using an ultrafiltration method, wherein the used instruments are an ultrafiltration cup and an ultrafiltration membrane, before the start of an experiment, respectively using a NaOH solution with the mass fraction of 50-60% and an HCl solution with the mass fraction of 60-70% to stir and clean the ultrafiltration membrane without pressurization, then adding deionized water to pressurize and stir and clean the ultrafiltration membrane, firstly performing ultrafiltration on 100 mL of ultrapure water before formal ultrafiltration, after the ultrafiltration is completed, taking a 10kDa ultrafiltration membrane at 25 ℃ for later use, putting 200 mL of the pretreated water sample into the ultrafiltration cup to pass through the membrane in a pressurized manner, pressurizing by using nitrogen, collecting filtrate under the membrane, adding 10 mL of deionized water into the ultrafiltration cup when 50 mL of the pretreated water sample remains, then continuously performing pressure stirring and filtration to obtain 10 mL, then adding 10 mL of deionized water into the ultrafiltration cup, performing pressure stirring and filtration to obtain 10 mL, then pouring out the concentrated solution on the membrane and adding 150 mL of deionized water into the ultrafiltration cup, namely, the DOC solution is 10-100 kDa, 30 mL of deionized water is added into filtrate under the membrane to be regarded as 0.01-10 kDa DOC solution, the DOC solution is sequentially passed through the membrane according to the method, the sequence is 10kDa → 5 kDa → 1kDa, and finally four molecular weight segments of DOC are obtained: 0.1-1 kDa, 1-5 kDa, 5-10 kDa and 10-100 kDa to prepare four DOC sample solutions;
(3) fluorescence quenching titration experiment:
adding deionized water into the four DOC sample solutions for dilution until the concentration of all the DOC sample solutions is 1-10 mg.L-1In the range of (1), 30 mL of each DOC sample solution was taken and put into a conical flask, and 0.01 mol. L. of 0, 60, 120, 180, 240, 300. mu.L of each DOC sample solution was added dropwise into the conical flask-1The metal solution with different valence layer electronic configuration in the conical flask is respectively provided with metal ion concentrations of 0, 20, 40, 60, 80 and 100 mu mol.L-1Neglecting the concentration dilution effect, placing all samples in a constant-temperature oscillation box to avoid light and oscillate for 24 hours after titration to prepare an experimental solution;
(4) three-dimensional fluorescence spectrum scanning:
taking out the combined and balanced experimental solution, and setting the excitation wavelength and the emission wavelength ranges to be 220-450 nm and 290-600 nm respectively through three-dimensional fluorescence spectrum scanning to obtain three-dimensional fluorescence scanning data of all samples;
(5) parallel factor analysis:
performing parallel factor analysis on the three-dimensional fluorescence spectrum scanning data of all experimental solutions to obtain the maximum fluorescence intensity of different fluorescence components in each water sample;
(6) calculation of binding parameters:
the modified Stren-Volmer model is adopted to determine the binding parameters between the metal and the parallel factor analysis derived fluorescent component, and the calculation formula is as follows:
fitting a modified Stren-Volmer model: f0/（F0-F）=1/（f*K*CM）+1/f（1）。
2. The method for diagnosing the binding capacity of a soluble organic carbon and a metal with a different valence band electron configuration according to claim 1, wherein the pore size of the ultrafiltration membrane in the step (2) is 10kDa, 5 kDa and 1kDa, respectively.
3. The method for diagnosing the binding capacity of a soluble organic carbon and a metal with a different valence layer electronic configuration according to claim 1, wherein the metal solution in the step (3) is Cu2+、Pb2+And (3) solution.
4. The method for diagnosing the binding capacity of the soluble organic carbon and the metal with different valence layer electronic configuration according to claim 1, wherein the step (4) of scanning the three-dimensional fluorescence spectrum comprises the following specific steps:
(1) three-dimensional fluorescence spectrum scanning is carried out on the fluorescence spectrum analyzer, and the instrument is equipped with 1 cm quartz cuvette, adopts 150W xenon arc lamp as excitation light source, PMT voltage = 400V, and signal-to-noise ratio 110 ~ 220, response time are set as automatic, scanning speed: 60000 nm·min-1The excitation wavelength range lambda EX = 220-450 nm, the interval is 5 nm, the emission wavelength range lambda Em = 290-600 nm, the interval is 1 nm, and the scanning spectrum is used for automatic instrument correction;
(2) two-dimensional scanning and three-dimensional scanning are carried out by ultrapure water before the fluorescence of the experimental solution is measured, so as to carry out Raman scattering correction and contrast of fluorescence spectrum on the measurement result, wherein the unit of fluorescence intensity is R.U.
5. The method for diagnosing the binding capacity of a soluble organic carbon and a metal with a different valence layer electron configuration according to claim 1, wherein the specific steps of the parallel factor analysis in the step (5) are as follows:
(1) obtaining common fluorescent components of multiple DOCs by parallel factor analysis, carrying out parallel factor analysis on the processed fluorescent data set through MATLAB R2016a software, and determining the quantity of the fluorescent components through methods such as residual analysis, core consistency analysis and half-test;
(2) the obtained maximum fluorescence intensity of each fluorescent component can be compared with the quenching intensity of metal ions with different valence layer electronic configurations to different fluorescent components of DOC by comparing the maximum fluorescence intensities.
6. The method for diagnosing the binding capacity of a soluble organic carbon and a metal with different valence layer electron configuration as claimed in claim 1, wherein the step (6) of modifying the Stren-Volmer model includes:
F0is the fluorescence intensity at the start of titration, i.e., when no metal is added, and F is the metal concentration CMmol·L-1The fluorescence intensity of (b).
7. The method for diagnosing the binding capacity of a soluble organic carbon and a metal with different valence layer electron configuration as claimed in claim 1, wherein the step (6) of modifying the Stren-Volmer model includes:
and (3) taking logarithm of the conditional stability constant K and the ratio f of the fluorescent group participating in metal ion coordination to obtain a binding stability constant lgK.
8. The method as claimed in claim 1, wherein the modified Stren-Volmer model in step (6) has a numerical relationship of:
(1) calculating the ratio f of the fluorescent groups participating in the coordination of the metal ions through 1/f;
(2) the conditional stability constant K was calculated by 1/f x K and logarithmized to give the binding stability constant lgK.
9. The method as claimed in claim 8, wherein the lgK value in step (2) is indicative of the difference in binding ability between the DOC and the metal ion with different valence layer electron configuration.
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