CN117147505A - Method for detecting cadmium in water - Google Patents
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- CN117147505A CN117147505A CN202310831405.9A CN202310831405A CN117147505A CN 117147505 A CN117147505 A CN 117147505A CN 202310831405 A CN202310831405 A CN 202310831405A CN 117147505 A CN117147505 A CN 117147505A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 69
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000001514 detection method Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000012086 standard solution Substances 0.000 claims abstract description 17
- 238000005070 sampling Methods 0.000 claims abstract description 13
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012488 sample solution Substances 0.000 claims description 30
- 230000015556 catabolic process Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000523 sample Substances 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001228 spectrum Methods 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 208000003251 Pruritus Diseases 0.000 claims description 3
- 238000000295 emission spectrum Methods 0.000 claims description 3
- 230000007803 itching Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 238000011208 chromatographic data Methods 0.000 abstract description 5
- 238000011895 specific detection Methods 0.000 abstract description 3
- 150000001661 cadmium Chemical class 0.000 abstract 1
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010061481 Renal injury Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 231100000085 chronic toxic effect Toxicity 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000037806 kidney injury Diseases 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Optics & Photonics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for detecting cadmium in water, which particularly relates to the field of water quality detection and comprises the following steps: preparing a series of cadmium standard solutions and preparing an up-conversion luminescent material; adding up-conversion luminescent materials into a series of prepared cadmium standard solutions to obtain detection solutions; establishing a cadmium content detection standard curve; sampling a water sample, and adding an up-conversion luminescent material into the water sample to obtain a water sample to be detected; substituting the data of the water sample to be detected into a standard curve to obtain the cadmium content concentration in the water sample to be detected. According to the invention, the fluorescent donor in the cadmium solution is used as the up-conversion luminescent material, a steady-state specific cadmium ion detection curve is constructed, chromatographic data appearing in the water sample is substituted into the characteristic curve, so that the accurate concentration of the cadmium content in the water sample can be obtained, the low-cost and high-sensitivity specific detection of the cadmium in the water sample is realized, and the comprehensive detection and comparison are performed by adopting a plurality of groups of water samples in a partitioned manner, so that the cadmium content in the water area is more effectively detected.
Description
Technical Field
The invention relates to the technical field of water quality detection, in particular to a method for detecting cadmium in water.
Background
Cadmium (Cd) is an accumulative heavy metal element that can be harmful to humans and other organisms even at very low concentration levels. Cadmium can accumulate in human body through food chain, and then cause various acute and chronic toxic effects of human body, which can cause damage of connective tissue injury, reproductive system dysfunction, kidney injury, teratogenesis and carcinogenesis, and even influence the growth and intelligence development of children.
Cadmium in the water environment has the characteristics of high toxicity, difficult metabolism, easy biological enrichment, biological amplification effect and the like, so that the cadmium pollution of the water environment seriously threatens the survival of aquatic organisms and the health of human beings. Therefore, monitoring and controlling cadmium content in water environments has become an important issue in relation to environmental protection, sustainable development and improvement of resident living standard.
The method for testing cadmium is many, such as a direct spectrophotometry method, a cadmium reagent method, a dithizone method and the like. The method has the defect of low accuracy for trace cadmium test, and the dithizone spectrophotometry (GB 7470-87) adopts lead in a slightly alkaline solution to react with dithizone to generate a red complex, and uses chloroform for extraction and colorimetry, and also needs to use a highly toxic reagent potassium cyanide and an organic reagent for extraction, so that the method is very complex in operation and serious in pollution, and the dithizone is very unstable and easy to deteriorate, and can influence the stability of the measurement of an analyzer. In addition, the flame atomic absorption method, the polarography and other instruments have higher cost and are difficult to realize and popularize.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a method for detecting cadmium in water, which aims to solve the problems that: the existing method for detecting cadmium in water has low precision and high cost.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method for detecting cadmium in water comprises the following steps:
s1: preparing a group of cadmium standard solutions with the same interval concentration, and preparing an up-conversion luminescent material, wherein the chemical formula of the up-conversion luminescent material is NaLu 1-x-y-z R x Yb y M z F 4 ；
S2: adding up-conversion luminescent materials into a series of prepared cadmium standard solutions, mixing and stirring until the solution is clarified to obtain a detection solution, and adding up-conversion luminescent materials, mixing and stirring until the solution is clarified to obtain a detection solution;
s3: the detection system is constructed, a laser-induced breakdown spectrometer is adopted to obtain the spectrum data of the detection solution obtained by mixing in the step S2, the characteristic value of the fluorescence intensity signal of the detection solution is measured according to the measurement, the concentration of cadmium ions is taken as an abscissa, the characteristic value of the fluorescence intensity signal is taken as an ordinate, and a cadmium content detection standard curve is established for each group of cadmium standard solutions;
s4: sampling water samples, determining a central point in a water area to be detected, sampling a plurality of groups of water samples, storing the water samples in corresponding containers to be used as sample solutions to be detected, mixing water sample extraction parts in the containers into the same container to be used as comprehensive sample solutions,
s5: water sample detection, namely adding up-conversion luminescent materials which are the same as those adopted for preparing the cadmium standard solution in the step S1 into each component sample solution and the comprehensive sample solution, mixing and stirring until the mixture is clear, and obtaining water samples to be detected corresponding to each group;
s6: and (3) measuring each group of water samples to be detected by using a laser-induced breakdown spectrometer to obtain spectrum data, substituting the data of each group of water samples to be detected into the standard curve obtained in the step (S3), and comparing to obtain the cadmium content concentration in each group of water samples to be detected.
S7: data recording, namely recording the measurement data of each component sample solution and the comprehensive sample solution seat respectively, calculating the average value of the measurement data of each component sample solution, comparing the average value with the measurement data of the comprehensive sample solution, and establishing a data chart with the sampling areas of the separated sample solutions and the corresponding sample solution concentrations
Preferably, in the step S1, R in the up-conversion luminescent material chemical formula is a rare earth element Y or any combination of Y, gd and La, and M is one or any combination of a plurality of rare earth elements Ho, er and Tm.
Preferably, in the chemical formula of the up-conversion luminescent material in the step S2, x, y and z are 0< x is less than or equal to 0.5, y is less than or equal to 0.1 and less than or equal to 0.5, and z is less than or equal to 0.1.
Preferably, in the step S2, the volume ratio of the up-conversion luminescent material to the cadmium standard solution is 0.5-1:3-8.
Preferably, step S2 is performed by adding up-conversion luminescent material into water area, heating for 3-5min, and measuring spectral data of detection solution.
Preferably, in step S4, a plurality of sampling points are obtained at fixed intervals on circumferences with the water area center point as the origin and diameters of 1m, 2m and 3m, itching is performed respectively, and a plurality of groups of water samples with different depths are collected in the water area corresponding to each point.
Preferably, the laser-induced breakdown spectrometer is excited by infrared light, and the emission spectrum range of the laser-induced breakdown spectrometer is 400-1000nm.
Preferably, the laser-induced breakdown spectrometer specifically measures the fluorescence intensity values at 547nm and 758nm under excitation of 980nm excitation light, denoted as I 547 And I 758 And I 547 And I 758 The ratio of (2) is the characteristic value of the fluorescence intensity signal of the detection solution, namely the ordinate of the cadmium content detection standard curve. .
The invention has the technical effects and advantages that:
according to the invention, the up-conversion luminescent material is used as a fluorescence donor in the cadmium solution, then different chromatographic data are displayed by the cadmium solutions with different solubilities, a steady-state specific cadmium ion detection curve is constructed, the chromatographic data displayed in the water sample are substituted into the characteristic curve, the accurate concentration of cadmium content in the water sample can be obtained, the low-cost and high-sensitivity specific detection of cadmium in the water sample is realized, the absorbance of the up-conversion luminescent material can be kept stable in the whole color development process, the rapid determination can be ensured, the method can be used for detecting the cadmium content of the water sample with any concentration, the detection step is simple, the high-efficiency and convenient by adopting the detection method, and the cadmium content of the water area can be more effectively detected by adopting a plurality of groups of water samples in a partitioning way and comprehensively detecting and comparing.
Drawings
FIG. 1 is a schematic flow chart of the detection method of the present invention;
FIG. 2 is a graph of a standard curve for detecting cadmium content in the detection method of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method for detecting cadmium in water provided by the embodiment of the invention comprises the following steps:
s1: preparing a group of cadmium standard solutions with the same interval concentration, and preparing an up-conversion luminescent material, wherein the chemical formula of the up-conversion luminescent material is NaLu 1-x-y-z R x Yb y M z F 4 ；
S2: adding up-conversion luminescent materials into a series of prepared cadmium standard solutions, mixing and stirring until the solution is clarified to obtain a detection solution, and adding up-conversion luminescent materials, mixing and stirring until the solution is clarified to obtain a detection solution;
s3: the detection system is constructed, a laser-induced breakdown spectrometer is adopted to obtain the spectrum data of the detection solution obtained by mixing in the step S2, the characteristic value of the fluorescence intensity signal of the detection solution is measured according to the measurement, the concentration of cadmium ions is taken as an abscissa, the characteristic value of the fluorescence intensity signal is taken as an ordinate, and a cadmium content detection standard curve is established for each group of cadmium standard solutions;
s4: sampling water samples, determining a central point in a water area to be detected, sampling a plurality of groups of water samples, storing the water samples in corresponding containers to be used as sample solutions to be detected, mixing water sample extraction parts in the containers into the same container to be used as comprehensive sample solutions,
s5: water sample detection, namely adding up-conversion luminescent materials which are the same as those adopted for preparing the cadmium standard solution in the step S1 into each component sample solution and the comprehensive sample solution, mixing and stirring until the mixture is clear, and obtaining water samples to be detected corresponding to each group;
s6: and (3) measuring each group of water samples to be detected by using a laser-induced breakdown spectrometer to obtain spectrum data, substituting the data of each group of water samples to be detected into the standard curve obtained in the step (S3), and comparing to obtain the cadmium content concentration in each group of water samples to be detected.
S7: data recording, namely recording the measurement data of each component sample solution and the comprehensive sample solution seat respectively, calculating the average value of the measurement data of each component sample solution, comparing the average value with the measurement data of the comprehensive sample solution, and establishing a data chart with the sampling areas of the separated sample solutions and the corresponding sample solution concentrations
Further, in the step S1, R in the up-conversion luminescent material chemical formula is any combination of rare earth element Y or Y and Gd, la, and M is one or any combination of a plurality of rare earth elements Ho, er, tm.
Further, in the chemical formula of the up-conversion luminescent material in the step S2, x, y and z are 0< x is less than or equal to 0.5, y is more than or equal to 0.1 and less than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.1.
Further, in the step S2, the volume ratio of the up-conversion luminescent material to the cadmium standard solution is 0.5-1:3-8.
Further, step S2 is to add up-conversion luminescent material water area to heat for 3-5min, and then to measure the spectrum data of the detection solution.
Further, in step S4, a plurality of sampling points are obtained at fixed intervals on circumferences with the water area center point as an origin and diameters of 1m, 2m and 3m, itching is performed respectively, and a plurality of groups of water samples with different depths are collected in the water area corresponding to each point.
Furthermore, the laser-induced breakdown spectrometer is excited by infrared light, and the emission spectrum range of the laser-induced breakdown spectrometer is 400-1000nm.
Further, the laser-induced breakdown spectrometer specifically measures the fluorescence intensity values at 547nm and 758nm under excitation of 980nm excitation light, and is denoted as I 547 And I 758 And I 547 And I 758 The ratio of (2) is the characteristic value of the fluorescence intensity signal of the detection solution, namely the ordinate of the cadmium content detection standard curve. .
To sum up: according to the invention, the up-conversion luminescent material is used as a fluorescence donor in the cadmium solution, then different chromatographic data are displayed by the cadmium solutions with different solubilities, a steady-state specific cadmium ion detection curve is constructed, the chromatographic data displayed in the water sample are substituted into the characteristic curve, the accurate concentration of cadmium content in the water sample can be obtained, the low-cost and high-sensitivity specific detection of cadmium in the water sample is realized, the absorbance of the up-conversion luminescent material can be kept stable in the whole color development process, the rapid determination can be ensured, the method can be used for detecting the cadmium content of the water sample with any concentration, the detection step is simple, the high-efficiency and convenient by adopting the detection method, and the cadmium content of the water area can be more effectively detected by adopting a plurality of groups of water samples in a partitioning way and comprehensively detecting and comparing.
Finally: the foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The method for detecting cadmium in water is characterized by comprising the following steps:
s1: preparing a group of cadmium standard solutions with the same interval concentration and preparing an up-conversion luminescent material, wherein the chemical formula of the up-conversion luminescent material is NaLu 1-x-y-z R x Yb y M z F 4 ；
S2: adding up-conversion luminescent materials into a series of prepared cadmium standard solutions, mixing and stirring until the solution is clarified to obtain a detection solution, and adding up-conversion luminescent materials, mixing and stirring until the solution is clarified to obtain a detection solution;
s3: the detection system is constructed, a laser-induced breakdown spectrometer is adopted to obtain the spectrum data of the detection solution obtained by mixing in the step S2, the characteristic value of the fluorescence intensity signal of the detection solution is measured according to the measurement, the concentration of cadmium ions is taken as an abscissa, the characteristic value of the fluorescence intensity signal is taken as an ordinate, and a cadmium content detection standard curve is established for each group of cadmium standard solutions;
s4: sampling water samples, determining a central point in a water area to be detected, sampling a plurality of groups of water samples, storing the water samples in corresponding containers to be used as sample solutions to be detected, mixing water sample extraction parts in the containers into the same container to be used as comprehensive sample solutions,
s5: water sample detection, namely adding up-conversion luminescent materials which are the same as those adopted for preparing the cadmium standard solution in the step S1 into each component sample solution and the comprehensive sample solution, mixing and stirring until the mixture is clear, and obtaining water samples to be detected corresponding to each group;
s6: and (3) measuring each group of water samples to be detected by using a laser-induced breakdown spectrometer to obtain spectrum data, substituting the data of each group of water samples to be detected into the standard curve obtained in the step (S3), and comparing to obtain the cadmium content concentration in each group of water samples to be detected.
S7: and (3) data recording, namely recording the measurement data of each component sample solution and the comprehensive sample solution seat respectively, calculating the average value of the measurement data of each component sample solution, comparing the average value with the measurement data of the comprehensive sample solution, and establishing a data chart of the sampling areas of the separated sample solutions and the corresponding sample solution concentrations.
2. The method for detecting cadmium in water according to claim 1, wherein: in the step S1, R in the chemical formula of the up-conversion luminescent material is rare earth element Y or any combination of Y, gd and La, and M is one or any combination of a plurality of rare earth elements Ho, er and Tm.
3. The method for detecting cadmium in water according to claim 1, wherein: in the step S2, x, y and z in the chemical formula of the up-conversion luminescent material meet 0< x less than or equal to 0.5, y is more than or equal to 0.1 and less than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.1.
4. The method for detecting cadmium in water according to claim 1, wherein: the volume ratio of the up-conversion luminescent material to the cadmium standard solution in the step S2 is 0.5-1:3-8.
5. The method for detecting cadmium in water according to claim 1, wherein: and step S2, adding the up-conversion luminescent material into a water area to heat for 3-5min, and then measuring spectral data of the detection solution.
6. The method for detecting cadmium in water according to claim 1, wherein: in the step S4, taking the central point of the water area as the origin, and obtaining a plurality of sampling points with the diameters of 1m, 2m and 3m on the circumference respectively at fixed intervals, respectively performing itching, and taking a plurality of groups of water samples with different depths in the water area corresponding to each point.
7. The method for detecting cadmium in water according to claim 1, wherein: the laser-induced breakdown spectrometer is excited by infrared light, and the emission spectrum range of the laser-induced breakdown spectrometer is 400-1000nm.
8. The method for detecting cadmium in water according to claim 7, wherein: the laser-induced breakdown spectrometer specifically measures the fluorescence intensity values of 547nm and 758nm under 980nm excitation light, and is recorded as I 547 And I 758 And I 547 And I 758 The ratio of (2) is the characteristic value of the fluorescence intensity signal of the detection solution, namely the ordinate of the cadmium content detection standard curve.
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| CN202310831405.9A CN117147505A (en) | 2023-07-07 | 2023-07-07 | Method for detecting cadmium in water |
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| CN202310831405.9A CN117147505A (en) | 2023-07-07 | 2023-07-07 | Method for detecting cadmium in water |
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Application publication date: 20231201 |