CN114720447A - Multi-signal output method for measuring peroxymonosulfate concentration - Google Patents
Multi-signal output method for measuring peroxymonosulfate concentration Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 title claims abstract description 16
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- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 3
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a multi-signal output method for measuring the concentration of peroxymonosulfate, which is used for measuring the concentration of PMS in an actual water sample by establishing a standard curve and a linear regression equation of PMS measured by a fluorescence method and a UV-Vis spectrophotometry. The principle is based on the fact that Peroxymonosulfate (PMS) oxidizes 3,3',5,5' -Tetramethylbenzidine (TMB) to generate a color reaction under the catalysis of low-concentration cobalt ions, and therefore the fact that the absorbance of a sensing system at 654nm is gradually increased along with the increase of the concentration of PMS is shown, and meanwhile, the fluorescence emission peak of the TMB at 404nm is shifted and the intensity is changed. The concentration range of PMS determined by fluorescence spectroscopy was: 0.23-48.80 μ M, detection limit of 0.03 μ M; the concentration range of PMS measured by UV-vis spectrophotometry is as follows: 0.98-130.13 μ M, and the detection limit is 0.11 μ M. Compared with the existing PMS (permanent magnet system) determination method, the method has the following advantages: the color developing agent TMB which is simple, quick, low in the concentration of the used cobalt ions and safe is colorless; the multi-signal output enables the test result to be more accurate.
Description
Technical Field
The invention belongs to the technical field of analysis and determination, and particularly relates to a multi-signal output method for determining the concentration of peroxymonosulfate.
Background
Permonosulfate ions (PMS) are used as strong oxidants and are widely used in Advanced Oxidation Processes (AOPs) for degrading organic pollutants in soil and water. Therefore, in remediation processes for treating contaminated groundwater, wastewater and soil based on AOPs of PMS, the concentration of PMS is an important operating parameter for the degradation of organic pollutants, and it is necessary to monitor the change at specified time intervals to assess efficiency. PMS is also used in the fields of corrosion caused by sulfides in concrete sewers, organic synthesis, decontamination of protein contaminants, decontamination and disinfection of water, and in-situ chemical oxidation. The reaction condition can be further optimized by monitoring the concentration of PMS, and the utilization rate of PMS is improved. For example, the permanence (lifetime and diffusion distance) of PMS in aqueous materials can be studied by measuring the PMS kinetic model of consumption, which is crucial for the design of field applications for in situ chemical oxidation. In addition, the residual amount information of the PMS after water treatment is obtained, so that waste of an oxidant and release of redundant PMS into treated water can be avoided. In addition, the reaction mechanism can be investigated by the consumption of PMS. With the rapid expansion of the research of the PMS related technology and the application prospect thereof in the fields, a simple, rapid and sensitive method is urgently needed for accurately measuring the residual quantity in the PMS oxidation process and the trace PMS released into natural water.
At present, reported analytical methods for PMS quantification are very limited, mainly including iodometry, uv-vis spectrophotometry, fluorescence and liquid chromatography. Among these methods, liquid chromatography is considered to be an ideal measurement method because of its accuracy, reliability, high sensitivity and immunity to organic mechanisms and salt concentrations, but its further application is limited due to the disadvantages of expensive instruments, time consuming and cumbersome operations. Iodometry is inexpensive and easy to operate by non-professional personnel. However, this method has poor reproducibility and high detection limit. The ultraviolet-visible spectrophotometry has the advantages of simple operation, high accuracy, good reproducibility and low consumption rate of samples and reagents, but is easily interfered by other colored substances in the dyeing/decoloring reaction. Compared with the ultraviolet-visible spectrophotometry, the fluorescence method has higher sensitivity and is not easily interfered by colored substances. However, the existing fluorescence method for measuring PMS concentration all involves using high-concentration environment toxic substance Co2+. Therefore, it is necessary to combine UV-visible spectrophotometry with fluorescenceThe method has the advantages of being rapid, environment-friendly, simple and effective in PMS concentration measurement to monitor the concentration of PMS. However, the design of such detectors still faces challenges.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a multi-signal output method for measuring the concentration of peroxymonosulfate, which solves the problem that a fluorescence method for measuring the concentration of PMS in the prior art needs to use a high-concentration environment toxic substance Co2+And the problem that the output signal is single and the measurement result is not accurate enough.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
a multiple signal output method for determining the concentration of peroxymonosulfate comprising the steps of:
s1: construction of a sensing system for determining PMS:
mixing TMB solution with Co2+Fully and uniformly mixing the solution and 3-4 mL of acetic acid-sodium acetate buffer solution to obtain a sensing system for measuring the concentration of PMS; the TMB concentration after mixing is 0.01-0.15 mM, Co2+The concentration is 1-100 mu M, and the pH value of the acetic acid-sodium acetate buffer solution is 3.5-6.0; and measuring the fluorescence intensity thereofI 0 And ultraviolet absorption intensityA 0 ；
S2: drawing a standard curve of PMS concentration in the solution determined by a fluorescence method:
respectively adding PMS standard solutions with the same volume and different concentrations into the sensing system constructed by S1 to obtain sensing systems with different PMS concentrations, and measuring the fluorescence intensity of the sensing systems with different PMS concentrations after full reactionIAnd relative fluorescence intensity with PMS concentration as abscissa(s) ((I 0 -I）/IDrawing a standard curve for a vertical coordinate to obtain a standard curve regression equation (1);
s3: drawing a standard curve for measuring the concentration of PMS in the solution by using a UV-vis spectrophotometry method:
respectively adding PMS standard solutions with the same volume and different concentrations into the sensing system constructed by S1 to obtain sensing systems containing different PMS concentrationsAfter full reaction, measuring the ultraviolet absorption intensity of the sensing system containing different PMS concentrations, and taking the PMS concentration as an abscissa, and measuring the relative ultraviolet absorption intensity deltaA Drawing a standard curve for the ordinate to obtain a standard curve regression equation (2);
s4: adding a sample to be detected into a sensing system of S1 for sufficient reaction, measuring the relative fluorescence intensity, bringing the measured relative fluorescence intensity into a standard curve regression equation (1), and calculating to obtain the concentration of PMS;
s5: and adding a sample to be detected into a sensing system of S1 for sufficient reaction, measuring the relative ultraviolet absorption intensity, substituting the measured relative ultraviolet absorption intensity into a standard curve regression equation (2), and calculating to obtain the concentration of PMS.
Further, the excitation wavelength for measuring the fluorescence intensity was 305nm, and the emission wavelength was 404 nm; the wavelength at which the ultraviolet absorption intensity was measured was 654 nm.
Furthermore, the S2 contains sensing systems with different PMS concentrations, and the concentration of PMS is 0.23-48.80 mu M.
Further, the standard curve regression equation (1) is y = 0.0701 + 0.2594x, R = 0.9993; wherein y is (I 0 -I）/IX is PMS concentration in μ M and R is a correlation coefficient.
Furthermore, the S3 contains sensing systems with different PMS concentrations, and the concentration of PMS is 0.98-130.13 mu M.
Further, the regression equation (2) of the standard curve is y = 0.0070 + 0.0129x, R = 0.9994; wherein y is ΔAX is PMS concentration in μ M and R is a correlation coefficient.
Further, the sufficient reaction time of S2 and S4 was 15 min.
Further, the sufficient reaction time of S3 and S5 was 20 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is based on the traditional TMB color development system, does not need complicated chemical synthesis process, has simple operation, does not need expensive chemical reagent and instrument, and uses Co2+At a concentration of 5. mu.M, is reportedOne tenth to one two hundredth of the use amount of the method is more environment-friendly.
2. When the concentration of the PMS is detected, the output signal is a double signal output of fluorescence intensity and ultraviolet absorption light intensity, and compared with the traditional single signal output detection method, the detection speed is more sensitive, and the detection result is more accurate.
3. The invention combines the dual-mode analysis of rapid 'prejudgment' and 'accurate' measurement, and establishes a method for measuring PMS by combining naked eye visual 'prejudgment' and accurate fluorescence detection. The dual-mode analysis method accelerates the detection speed, reduces the detection cost and improves the detection accuracy.
4. The method established by the invention has good anti-interference capability and strong practicability, can sensitively detect the PMS in the presence of common ions, organic substances, humic acid and hydrogen peroxide in the environment, and can be used for simply and rapidly detecting the PMS in the actual water environment. The invention has good application prospect and potential application value in the field of detection and analysis.
Drawings
FIG. 1 is a schematic diagram of the detection method of the present invention;
FIG. 2 is a graph showing the variation of PMS and fluorescence intensity at different concentrations;
FIG. 3 is a graph showing the variation of intensity of PMS and UV absorption spectra at different concentrations;
FIG. 4 is a graph of the effect of common cations or anions in an aqueous environment on the determination of PMS;
FIG. 5 shows the effect of common organic substances in water environment on PMS determination.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described with reference to the following specific examples, but the embodiments of the present invention are not limited thereto.
TMB: 3,3',5,5' -tetramethylbenzidine;
PMS: a salt of peroxymonosulfate.
The detection method comprises the following steps: adding PMS-containing solution into mixed solution containing TMB and cobalt ions; after fully and uniformly mixing, measuring a fluorescence emission spectrum and an ultraviolet absorption spectrum within the range of 500-800 nm under the condition that the excitation wavelength is set to be 305 nm; and respectively substituting the obtained relative fluorescence intensity and the obtained relative ultraviolet absorption intensity into respective standard curves to calculate the PMS content of the solution to be measured.
The detection principle of the invention (as shown in fig. 1): by TMB-Co2+Novel method for system establishment of dual signal output PMS, specifically Co2+As PMS activator, TMB as chemical probe. PMS is at low concentration of 1-100 mu MCo2+Sulfate free radicals are generated under the catalysis, and the generated sulfate free radicals and colorless TMB undergo oxidation-reduction reaction to generate a blue TMB oxidation product. As the concentration of PMS is increased, the intensity of the fluorescence emission peak of TMB at 404nm is reduced, and simultaneously, the intensity of the ultraviolet absorption peak of TMB oxidation products at 654nm is increased. Based on this, Co is simple, fast and only needs low concentration2+The sensing system is configured for a sensitive and selective determination of PMS concentration in an aqueous solution with dual signal outputs.
Method for measuring PMS
Example 1
1) Drawing a standard curve for measuring the concentration of PMS in the solution by a fluorescence method:
mixing 0.01-0.15 mM TMB and 1-100 μ M Co2+Mixing with 4 mL of acetic acid-sodium acetate buffer solution with pH of 3.5-6.0, adding 20 μ L of PMS standard solutions with different concentrations into the mixed solution to obtain mixed solution containing different PMS concentrations, wherein the final concentration of PMS is 0.00 μ M, 0.23 μ M, 0.33 μ M, 0.65 μ M, 1.30 μ M, 1.95 μ M, 2.60 μ M, 3.25 μ M, 9.76 μ M, 16.27 μ M, 22.77 μ M, 32.53 μ M, 48.80 μ M, and measuring fluorescence intensity at excitation wavelength of 305nm and emission wavelength of 404nm respectively after mixing reaction for 15 min, and relative fluorescence intensity is measured (relative fluorescence intensity) with PMS concentration as abscissa (concentration of X is: (A) ((M)I 0 -I）/IDrawing a standard curve for the ordinate; wherein,I 0 the fluorescence intensity of the sensing system is when the concentration of PMS is zero,Ithe results are shown in fig. 2 for the corresponding fluorescence intensities for the sensing system in the presence of different concentrations of PMS.
It can be seen from the figure that the fluorescence intensity of the sensing system decreases with increasing concentration of PMS, indicating that the sensing system can be used for the determination of PMS.
When the concentration of PMS is in the range of 0.23-48.80 mu M, the regression equation of the standard curve is y = 0.0701 + 0.2594x, and R = 0.9993;
wherein y is (I 0 -I）/IX is PMS concentration in μ M and R is a correlation coefficient.
2) Drawing a standard curve for measuring the concentration of PMS in the solution by using a UV-vis spectrophotometry method:
mixing 0.01-0.15 mM TMB and 1-100 μ M Co2+Mixing with 4 mL of acetic acid-sodium acetate buffer solution with pH of 3.5-6.0, adding 20 μ L of PMS standard solutions with different concentrations into the mixed solution to obtain mixed solution containing different PMS concentrations, wherein the final concentration of PMS is 0.00 μ M, 0.98 μ M, 1.63 μ M, 9.76 μ M, 16.27 μ M, 22.77 μ M, 32.53 μ M, 48.80 μ M, 65.07 μ M, 81.33 μ M, 97.60 μ M, 113.87 μ M, 130.13 μ M, mixing and reacting for 20 min, and measuring ultraviolet absorption intensity at 654nm, with PMS concentration as abscissa and relative absorption intensity ΔA (ΔA =A - A 0 ) Drawing a standard curve for the ordinate; wherein,A 0 the absorption strength of the sensing system when the concentration of PMS is zero,Athe results are shown in fig. 3 for the corresponding absorption strength of the sensing system in the presence of PMS of different concentrations.
It can be seen from the figure that the ultraviolet absorption intensity of the sensing system increases with increasing concentration of the PMS, indicating that the sensing system can be used for the determination of PMS.
When the concentration of PMS is in the range of 0.98-130.13 mu M, the regression equation of the standard curve is y = 0.0070 + 0.0129x, and R = 0.9994;
wherein y is ΔAX is PMS concentration in μ M and R is a correlation coefficient.
3) And (3) determination of a sample to be tested:
0.5 mL of solution(s) of pefloxacin, ticarcillin, ciprofloxacin, levofloxacin and rhodamine B which are subjected to PMS advanced oxidative degradation treatment are respectively usedPMS remained in the solution after PMS advanced oxidative degradation treatment), and the solution was added to 3.0 mL of a solution containing 0.01 mM of TMB and 5. mu.M of Co2+After fully mixing the solution in the pH 5.2 acetic acid-sodium acetate buffer solution for 15 min, measuring the fluorescence intensity at the excitation wavelength of 305nm and the emission wavelength of 404nm, and obtaining the concentration of the residual PMS in the antibiotic and dye solution after the advanced oxidative degradation treatment according to the regression equation of a standard curve, wherein the concentration of the residual PMS is y = 0.0701 + 0.2594x, and the measurement result is the same as that of the KI spectroscopy.
Respectively adding 0.5 mL of solution after being treated by advanced oxidative degradation with pefloxacin, ticarcillin, ciprofloxacin, levofloxacin and rhodamine B into 3.0 mL of solution containing 0.15 mM of TMB and 5 mu M of Co2+After fully mixing the solution in pH 5.2 acetic acid-sodium acetate buffer solution for 20 min, measuring the ultraviolet absorption intensity at 654nm, and obtaining the concentration of the residual PMS in the antibiotic and dye solution after the advanced oxidative degradation treatment according to the standard curve regression equation of y = 0.0070 + 0.0129x, wherein the measurement result is the same as that of KI spectroscopy.
Therefore, the new method based on dual signal output can be used for the determination of PMS in real samples.
Second, influence of other ions and organic matters on PMS determination in water environment
(1) In a solution containing 32.53. mu.M PMS, 0.05 mM TMB and 5. mu.M Co2+Adding different anions and cations into the acetic acid-sodium acetate buffer solution with the pH of 5.2 to obtain 20000.00 mu M Na+, 10000.00 μM K+, 650.00 μM Ba2+, 650.00 μM Zn2+, 650.00 μM Cu2+, 650.00 μM Mg2+, 650.00 μM Mn2+, 650.00 μM Pb2+, 650.00 μM Ca2+, 35.00 μM Al3+, 35.00 μM Fe3+, 10000.00 μM SO4 2−, 10000.00 μM Cl-, 1300.00 μM NO3 −, 650.00 μM CO3 2−, 350.00 μM PO4 3−(the final concentration is not specifically shown). After mixed reaction for 20 min, the fluorescence intensity is measured at the excitation wavelength of 305nm and the emission wavelength of 404nm respectivelyThe UV absorption intensity was measured at degree and 654nm, as shown in FIG. 4.
As can be seen from the figure, after other common cations and anions are added, the fluorescence intensity and the ultraviolet absorption intensity are measured at the same wavelength, the intensity fluctuation is small, and the influence of the other common cations and anions on the measurement result of PMS measurement is small and can be almost ignored, which shows that the method has good anti-interference capability on PMS detection, and the other common cations or anions in the water environment can not generate interference on PMS measurement. Therefore, the method is suitable for measuring the content of the PMS in the actual water environment.
(2) In a solution containing 32.53. mu.M PMS, 0.05 mM TMB and 5. mu.M Co2+To the acetic acid-sodium acetate buffer solutions of pH 5.2 were added different common organic substances to give final concentrations of 1.00 ppm Humic Acid (HA), 20.0 ppm Bovine Serum Albumin (BSA), 20.00 ppm dextran (Dex), 20.80 ppm methanol (MeOH), 29.90 ppm Formic Acid (FA), 19.50 ppm formaldehyde (Formal), 57.20 ppm Ethyl Acetate (EAC), 73.45 ppm chlorobenzene (Chl) (not specifically mentioned, all indicate final concentrations). After mixing and reacting for 20 min, the fluorescence intensity at the excitation wavelength of 305nm, the emission wavelength of 404nm and the ultraviolet absorption intensity at 654nm were measured, respectively, as shown in FIG. 5.
As can be seen from the figure, after other common organic matters are added, the fluorescence intensity and the ultraviolet absorption intensity are measured at the same wavelength, the intensity fluctuation is small, and the influence of the other common organic matters on the measurement result of PMS measurement is small and can be almost ignored, which shows that the method has good anti-interference capability on PMS detection, and the other common organic matters in the water environment can not generate interference on PMS measurement. Therefore, the method is suitable for measuring the content of the PMS in the actual water environment.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (8)
1. A multiple signal output method for determining the concentration of peroxymonosulfate comprising the steps of:
s1: constructing a sensing system for determining PMS:
mixing TMB solution with Co2+Fully and uniformly mixing the solution and 3-4 mL of acetic acid-sodium acetate buffer solution to obtain a sensing system for measuring the concentration of PMS; the mixed TMB concentration is 0.01-0.15 mM, Co2+The concentration is 1-100 mu M, and the pH value of the acetic acid-sodium acetate buffer solution is 3.5-6.0; and measuring the fluorescence intensity thereofI 0 And ultraviolet absorption intensityA 0 ；
S2: drawing a standard curve for measuring the concentration of PMS in the solution by a fluorescence method:
respectively adding PMS standard solutions with the same volume and different concentrations into the sensing system constructed by S1 to obtain sensing systems with different PMS concentrations, and measuring the fluorescence intensity of the sensing systems with different PMS concentrations after full reactionIAnd relative fluorescence intensity with PMS concentration as abscissa (1I 0 -I）/IDrawing a standard curve for a vertical coordinate to obtain a standard curve regression equation (1);
s3: drawing a standard curve for measuring PMS concentration in the solution by using a UV-vis spectrophotometry:
respectively adding PMS standard solutions with the same volume and different concentrations into a sensing system constructed by S1 to obtain sensing systems with different PMS concentrations, measuring the ultraviolet absorption intensity of the sensing systems with different PMS concentrations after full reaction, and taking the PMS concentration as a horizontal coordinate and the relative ultraviolet absorption intensity deltaA Drawing a standard curve for the ordinate to obtain a standard curve regression equation (2);
s4: adding a sample to be detected into a sensing system of S1 for sufficient reaction, measuring the relative fluorescence intensity, bringing the measured relative fluorescence intensity into a standard curve regression equation (1), and calculating to obtain the concentration of PMS;
s5: and adding the sample to be detected into a sensing system of S1 for sufficient reaction, measuring the relative ultraviolet absorption intensity, bringing the measured relative ultraviolet absorption intensity into a standard curve regression equation (2), and calculating the concentration of the PMS.
2. The multiple-signal outputting method for measuring the concentration of peroxymonosulfate according to claim 1, wherein the excitation wavelength for measuring the fluorescence intensity is 305nm, and the emission wavelength is 404 nm; the wavelength at which the ultraviolet absorption intensity was measured was 654 nm.
3. The multiple signal output method for determining the concentration of peroxymonosulfate as claimed in claim 2, wherein the sensing system with different PMS concentrations is contained in S2, and the PMS concentration is 0.23-48.80 μ M.
4. The multiple signal output method for determining the concentration of peroxymonosulfate of claim 3, wherein the standard curve regression equation (1) is y = 0.0701 + 0.2594x, R = 0.9993; wherein y is (I 0 -I）/IX is PMS concentration in μ M, and R is a correlation coefficient.
5. The multiple signal output method for determining the concentration of peroxymonosulfate as claimed in claim 2, wherein said S3 comprises sensing systems with different PMS concentrations, and the PMS concentration is 0.98-130.13 μ M.
6. The multiple signal output method for determining the concentration of peroxymonosulfate of claim 4, wherein standard curve regression equation (2) is y = 0.0070 + 0.0129x, R = 0.9994; wherein y is ΔAX is PMS concentration in μ M, and R is a correlation coefficient.
7. The multiple signal output method for determining the concentration of peroxymonosulfate of claim 1, wherein the sufficient reaction time of S2 and S4 is 15 min.
8. The multiple signal output method for determining the concentration of peroxymonosulfate of claim 1, wherein the sufficient reaction time of S3 and S5 is 20 min.
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