CN111103271B - Atomic fluorescence analysis method for outer tube sample injection - Google Patents
Atomic fluorescence analysis method for outer tube sample injection Download PDFInfo
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- CN111103271B CN111103271B CN201910227203.7A CN201910227203A CN111103271B CN 111103271 B CN111103271 B CN 111103271B CN 201910227203 A CN201910227203 A CN 201910227203A CN 111103271 B CN111103271 B CN 111103271B
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- 238000012921 fluorescence analysis Methods 0.000 title claims abstract description 36
- 238000002347 injection Methods 0.000 title claims abstract description 26
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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
- G01N21/6404—Atomic 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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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
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
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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
- G01N21/6404—Atomic fluorescence
- G01N2021/6406—Atomic fluorescence multi-element
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- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to an atomic fluorescence analysis method of outer tube sample injection, belonging to the atomic fluorescence analysis in the field of analytical chemistry. The invention utilizes the original quartz furnace to implement outer tube sample injection, the hydrogen flame is easy to ignite, the detection sensitivity is improved, and the invention is an innovation of the atomic fluorescence analysis technology.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and relates to atomic fluorescence analysis. The method changes the traditional sample injection mode and the corresponding technology of an atomizer in atomic fluorescence analysis, and particularly relates to the improvement of the sample injection method in the original atomic fluorescence analysis method.
Background art scene
Atomic fluorescence analysis has been widely used for the determination of trace amounts of As, Sb, Bi, Hg, Se, and the like. The basic principle is that ions of an element to be detected in an acidic medium (usually hydrochloric acid) react with a strong reducing agent (usually potassium borohydride or sodium borohydride) to be reduced into gaseous hydride or atoms, and a large amount of hydrogen is generated. The hydride molecules are dissociated into ground state atoms in the high-temperature hydrogen flame and excited to a high energy state by radiation of a specific frequency of an excitation light source, and the excited state atoms emit fluorescence of a characteristic wavelength in the form of light radiation in the de-excitation process due to extreme instability of the high energy level. The fluorescence intensity is correlated with the concentration of the element to be detected, and the concentration of the element to be detected is obtained by measuring the fluorescence signal intensity of the element to be detected by a detector (usually a photomultiplier).
The atomic fluorescence analysis device (also called atomic fluorescence instrument and atomic fluorescence photometer) designed according to the principle mainly comprises a transfusion system, a steam generation system (or called reactor), an atomizer, an excitation light source and a detection system. The test solution and the reducing agent are conveyed through the liquid conveying system and are carried by carrier liquid (also called carrier liquid) to be fed into the reactor to carry out chemical reaction to generate gaseous hydride molecules and hydrogen, and the gaseous hydride molecules and the hydrogen enter the atomizer under the carrying of the carrier gas (usually argon).
The atomization of hydride relies on the high temperature of the hydrogen flame, and the atomization process is performed by reference to a quartz furnace in an atomizer. Referring to fig. 1, a conventional quartz furnace is in the form of a sleeve, and includes a central tube (inner tube) and an outer tube, a carrier gas (argon) carrying hydride and hydrogen gas is led out from the central tube deep into the quartz furnace, a shielding gas (argon) is inputted from the outer tube, and the hydride led out from the central tube is atomized in an ignited hydrogen flame (shielding gas argon shield). The stable and slender hydrogen flame can be obtained by carrying with small flow carrier gas (Ar gas), the furnace wire for igniting the hydrogen is positioned at the pipe orifice of the outer pipe, and the hydrogen flame can not be ignited because the pipe orifice of the central pipe of the quartz furnace is positioned in the quartz furnace and is away from the pipe orifice of the outer pipe of the quartz furnace at a certain distance, especially for the elements generating less hydrogen in the reaction. This is an obstacle for atomic fluorometers to measure these elements.
Disclosure of Invention
The invention aims to provide an atomic fluorescence analysis method for outer tube sample injection, which is used for effectively solving the problems in atomic fluorescence analysis.
The atomic fluorescence analysis method for outer tube sample injection comprises the steps of sampling and conveying, feeding mixed gas generated by a carrier gas carrying gas-liquid separator into an atomizer, atomizing elements to be detected, detecting fluorescence and the like, wherein a quartz furnace in the atomizer is of a sleeved structure of an inner tube and an outer tube, the mixed gas is introduced into the outer tube of the quartz furnace, and auxiliary gas is introduced into the inner tube of the quartz furnace.
In the atomic fluorescence analysis method for outer tube sample injection, the carrier gas flow rate of the carrier gas mixture entering the outer tube of the quartz furnace is 1000-1200 ml/min.
In the atomic fluorescence analysis method for external tube sample injection, the flow rate of the auxiliary gas introduced into the internal tube of the quartz furnace is 400-600 ml/min. Alternatively, the flow rate of the auxiliary gas introduced into the inner tube of the quartz furnace is 0 ml/min.
In the atomic fluorescence analysis method for outer tube sample injection, the carrier gas for carrying the mixed gas to enter the outer tube of the quartz furnace is argon. The auxiliary gas is an inert gas, preferably the same gas as the carrier gas, such as argon.
The atomic fluorescence analysis method for outer tube sample injection comprises the following operation steps:
the operation 1, a gas outlet branch pipe (hydride, hydrogen and carrier gas mixed gas) of a gas-liquid separator is connected into an outer pipe of a quartz furnace of an atomizer, and meanwhile, an inner pipe of the quartz furnace is connected with auxiliary gas;
2, switching on a power supply of the atomic fluorescence instrument, selecting a single-channel mode or a double-channel mode on a setting page of a desktop system, confirming conditions required by testing, lighting an excitation light source of an element to be tested and preheating;
The element to be tested is one, and the single-channel mode is set in the operation 2.
Or, the number of the elements to be detected is two, and a dual-channel mode is set in the operation 2 (two excitation light sources work simultaneously).
In operation 5, the standard series solution contains two elements, fluorescence signal values of the two elements are obtained after the same sample solution is injected, standard curves of fluorescence value-concentration are made for the two elements after the standard series solution is measured, and the concentrations of the corresponding elements to be measured in the sample solution are obtained from the two standard curves respectively.
By adopting the scheme, the structure of the original atomizer is not changed in the atomic fluorescence analysis process, the sample injection of the outer tube is implemented by utilizing the prototype quartz furnace, the defect of the sample injection of the inner tube is overcome, hydrogen is heated by a furnace wire positioned at the tube opening of the outer tube, the hydrogen flame is very easy to ignite, the formed hydrogen flame is large and stable in shape, and the determination sensitivity is obviously improved. Experiments prove that the outer tube sample injection mode is particularly suitable for generating elements with less hydrogen, and solves the problem in the prior atomic fluorescence detection.
The invention is described in detail below with reference to the figures and examples.
Drawings
FIG. 1 is a schematic diagram of the original sample injection mode of a quartz furnace in atomic fluorescence analysis;
FIG. 2 is a schematic diagram of the outer tube sample injection method of the present invention in atomic fluorescence analysis;
FIG. 3 is a graph of example 1, which shows the peak value curve (A, fluorescence value-time) of Cd measured by the atomic fluorescence analysis method using outer tube sampling and the standard curve (B, fluorescence value-concentration) of Cd 0.1-0.5 ng/mL;
FIG. 4 is a graph showing the peak value curve (A, fluorescence value vs. time) of Hg/As measured simultaneously with the atomic fluorescence analysis method of the present invention using the outer tube for external sample injection and the standard curve (B, fluorescence value vs. concentration) of a mixed solution of 0.1 to 0.5ng/ml Hg for Hg and 10 to 50ng/ml As for As.
FIG. 5 is a graph showing the peak value of Pb (A, fluorescence value vs. time) and the standard curve of Pb 2-10ng/mL (B, fluorescence value vs. concentration) measured by the atomic fluorescence analysis method using the outer tube of the present invention in example 1;
Detailed Description
The invention discloses an atomic fluorescence analysis method for outer tube sample injection. Referring to fig. 2 and comparing with fig. 1, the method comprises the steps of changing a mixed gas (generated in a gas-liquid separator) of hydride and hydrogen carried by a carrier gas (argon) originally connected with an inner tube of a quartz furnace to an outer tube, and changing a shielding gas (Ar gas) tube of the outer tube to an inner tube as an auxiliary gas; on the other hand, the flow rate of the carrier gas (also Ar gas) carrying the mixed gas is increased to 1000-1200ml/min, the flow rate of the shielding gas (Ar gas) is reduced from 1000ml/min in the original mode to 400-600ml/min, and some elements can be measured even without introducing the auxiliary gas (i.e. 0 ml/min).
The invention changes the mode of introducing hydride (or Hg atoms) from the inner tube in the atomic fluorescence method. The mechanism is as follows: gaseous atoms or molecules and hydrogen generated by the chemical reduction reaction are introduced from the outer tube of the quartz furnace along with the carrier gas Ar gas carrier, the mixed gas of the element hydride (or mercury atoms) to be detected and the hydrogen rises along the inner wall of the outer tube of the quartz furnace, the hydrogen is immediately ignited by heating at the mouth of the quartz furnace, and the hydride is dissociated under the action of oxyhydrogen flame at high temperature in the Ar gas atmosphere. The auxiliary gas (usually argon) entering the inner tube pulls the hydrogen flame upward, and the hydrogen flame formed is much larger than the inner tube sample, as shown in fig. 2.
The sample introduction mode is combined with the original atomic fluorescence analysis process, and the method is successfully used for determining As, Hg, Se, Pb and Cd in various samples, improves the determination sensitivity of the atomic fluorescence method, and solves the problem of determining trace elements such As Pb and the like by the atomic fluorescence analysis.
The existing atomic fluorescence instrument can be utilized in the detection, the atomic fluorescence instrument comprises a sample injection system, a gas-liquid separator, an atomizer, an excitation light source and a detector, and the specific operation of the detection example of the atomic fluorescence instrument is as follows:
2, switching on a power supply of the atomic fluorescence instrument, selecting a single channel or a double channel on a setting page of a desktop system, confirming conditions required by the test, lighting an excitation light source of an element to be tested and preheating for 5-10 minutes;
The above method can measure a single element, and can also measure two or more elements simultaneously. When the multi-element is measured, a standard mixed solution containing all elements (the concentrations of all elements can be different) is prepared, samples are fed once, the exciting light action samples corresponding to all elements are synchronously used, the fluorescence signal values of different elements are respectively obtained, and the content of the element to be measured in the sample is obtained according to the standard curve of the corresponding element.
The present invention is further illustrated by the following specific examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention. In the examples, "%" of the reagent concentration is expressed as mass percent concentration.
Example 1: analysis of Cd
Testing a sample: rice, soybean
And (3) manufacturing a cadmium standard curve: preparing 10ng/ml cadmium standard solution (prepared now), then respectively putting 0, 0.5, 1.0, 1.5, 2.0 and 2.5ml of the standard solution into a 50ml plastic quantitative bottle, respectively adding 4ml of 50% HCl solution and 5ml of 5% thiourea into each solution, diluting the solutions to a scale with water, wherein the concentrations of the standard series solutions are 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng/ml Cd. After shaking up, the fluorescence signals of the blank and standard series solutions were measured according to the procedure to prepare a standard curve (see FIG. 3B, the slope of the standard curve exceeds 4000/ng/ml. A is the peak curve of Cd). During operation, the carrier gas and the auxiliary gas are Ar gas, the flow rate of the argon gas (outer tube) as the carrier gas is controlled to be 1000-1200ml/min, and the argon gas (flow rate is 0ml/min) as the auxiliary gas in the inner tube is closed.
Preparation and determination of test solutions: weighing 0.1-0.2g of rice or soybean sample, placing the rice or soybean sample in a 50ml plastic quantitative bottle, adding 50% HCl 4ml and 5% thiourea 5ml respectively, shaking for 5-10min, diluting with water to scale, shaking uniformly, measuring the fluorescence signal of the sample solution by using the sample solution as a test solution according to the same operation as that in the standard curve measurement, and obtaining the concentration of Cd from the standard curve and converting the concentration of Cd into the content of Cd in the sample. The results of the determination of Cd in the food samples are shown in Table 1.
TABLE 1 test results (ng/g) for Cd in rice and soybean meal
As can be seen from the data in the table, although the sample weighing (G) is greatly different, cadmium in rice and other foods can be rapidly determined by using the atomic fluorescence analysis of outer tube sample injection, and the content of Cd in the measured sample is consistent with the recommended value.
Example 2: simultaneous measurement of Hg/As
Testing a sample: soil(s)
Because the content of As in soil is much higher than Hg, the existing atomic fluorescence instrument can not simultaneously measure Hg and As in the sample. In this embodiment, the outer tube sample injection atomic fluorescence detection technology realizes the simultaneous detection of two elements of Hg and As in the same sample.
And (3) preparing a standard curve: a mixed standard solution containing 500ng/ml As and 5ng/ml Hg was prepared in advance. Taking 0, 1, 2, 3, 4 and 5ml of the standard solution respectively, putting 5ml of 5% Vc-5% thiourea solution and 10ml of HCl with the concentration of 50% in 50ml plastic quantitative bottles, diluting the solutions to a scale with water, and obtaining series of standard solutions with the Hg concentration of 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng/ml and the As concentration of 0, 10, 20, 30, 40 and 50 ng/ml.
Selecting a double-channel mode (respectively provided with excitation light sources corresponding to Hg and As), simultaneously measuring fluorescence signals of Hg and As in blank and standard series solutions according to the operation process, and respectively making standard curves of 0.1-0.5ng/ml Hg and 10-50ng/ml As of the mixed standard solution. The A panel of FIG. 4 is the peak value curve of Hg/As, and the B panel of FIG. 4 is the standard curve of mixed standard solution Hg and As (the signal of the standard curve is calculated from the spectrum area, and the blank area has been subtracted). In the operation, the carrier gas and the auxiliary gas are Ar gas, the flow rate of the argon (outer tube) as the carrier gas is controlled to be 1000-1200ml/min, and the flow rate of the argon (inner tube) as the auxiliary gas is controlled to be 400-600 ml/min.
Preparation and determination of test solutions: 0.1-0.2g of soil sample is placed in a 50ml plastic quantitative bottle, 5ml of 5% Vc-5% thiourea solution and 10ml of HCl with the concentration of 50% are added, the mixture is diluted to a scale with water, after shaking up, the sample solution is used As a test solution, fluorescence signals of Hg and As of the sample solution are simultaneously measured according to the same operation As that in the standard curve measurement, and the concentration of corresponding elements is obtained according to respective standard curves, so that the content of the corresponding elements in the sample is calculated. The results are shown in Table 2.
TABLE 2 results of simultaneous measurement of soil Hg/As
The data show that the difficulty of simultaneously measuring Hg and As in soil is solved using the present method and apparatus. Meanwhile, the Hg content in 6 samples (standard samples) is greatly different, but the test results are consistent with recommended values, which indicates that the atomic fluorescence analysis method is high in accuracy. In addition, in the embodiment, two elements coexist in the test solution, sampling is completed at one time, detection of the double-channel detection system is also completed at one time, and the whole test process is rapid.
Example 3: analysis of Pb
Testing a sample: chemical reagents calcium chloride and calcium hydroxide
And (3) preparing a lead standard curve: preparing 100ng/ml lead standard solution, then respectively putting 0, 1, 2, 3, 4 and 5ml of the standard solution into a 50ml plastic quantitative bottle, respectively adding 10ml of 50% HCl solution and 5ml of 5% thiourea into each solution, and diluting the solutions to a scale by using water, wherein the concentrations of the standard series solutions are 0, 2, 4, 6, 8 and 10ng/ml Pb. After shaking, the fluorescence signals of the blank and standard series solutions were measured according to the procedure to prepare a standard curve (see FIG. 5B, A is a peak curve for Pb). In the operation, the carrier gas and the auxiliary gas are Ar gas, the flow rate of the argon (outer tube) as the carrier gas is controlled to be 1000-1200ml/min, and the flow rate of the argon (inner tube) as the auxiliary gas is controlled to be 400-600 ml/min.
Preparation and determination of test solutions: weighing 0.2-0.3g of chemical reagent sample, dissolving, transferring into a 50ml plastic quantitative bottle, adding 10ml of 50% HCl and 5ml of 5% thiourea, shaking for 5-10min, diluting with water to a scale, shaking uniformly, measuring a fluorescence signal of the sample solution by using the sample solution as a test solution according to the same operation as that in the standard curve measurement, and obtaining the concentration of Pb from the standard curve and converting the concentration of Pb into the content of Pb in the sample. The results of the determination of Pb in the chemical reagent are shown in Table 3.
TABLE 3 determination of Pb in calcium chloride and calcium hydroxide (ng/g)
The acidity of the original atomic fluorescence analysis needs to be strictly controlled to be 2% in the determination of Pb, otherwise, no fluorescence signal can be detected, but the pre-treated test solution is difficult to meet the requirement, and moreover, the 2% acidity test solution generates less hydrogen after the reduction reaction and is difficult to ignite. In the embodiment, the hydrogen flame is easy to ignite by using the mode of injecting sample from the outer tube and increasing the flow rate of carrier gas, and the atomic fluorescence analysis is performed on Pb in the test solution with 10% acidity, so that an obvious Pb peak curve (see B range in figure 5) can be formed, the detection sensitivity is improved, and the determination of Pb is realized.
Claims (9)
1. The hydride generation atomic fluorescence analysis method of the external tube sample introduction comprises the steps of sampling and conveying, feeding mixed gas containing element hydride to be detected, hydrogen and carrier gas generated by a carrier gas-carrying gas-liquid separator into an atomizer, atomizing the element to be detected and detecting fluorescence, and is characterized in that a quartz furnace in the atomizer is of a sleeved structure of an inner tube and an outer tube, a gas outlet branch tube of the gas-liquid separator is connected into the outer tube of the quartz furnace, the mixed gas containing the element hydride to be detected, the hydrogen and the carrier gas is introduced into the outer tube of the quartz furnace, meanwhile, an inert gas is connected into a tube in the quartz furnace, and the inert gas is introduced into the inner tube of the quartz furnace so as to stretch the hydrogen flame upwards; the element to be detected is As, Hg, Se, Pb or Cd.
2. The method as claimed in claim 1, wherein the flow rate of the carrier gas for carrying the mixed gas into the outer tube of the quartz furnace is 1000-1200 ml/min.
3. The method for hydride generation atomic fluorescence analysis by external tube injection as claimed in claim 1, wherein the flow rate of the inert gas introduced into the internal tube of the quartz furnace is 400-600 ml/min.
4. The method according to claim 1, wherein the carrier gas for carrying the mixed gas into the outer tube of the quartz furnace is argon.
5. The method according to claim 1, wherein the inert gas is the same gas as the carrier gas.
6. The hydride generation atomic fluorescence analysis method for the external tube sample injection according to claim 1, characterized by comprising the following steps: the method comprises the following steps that 1, a gas outlet branch pipe of a gas-liquid separator is connected into an outer pipe of a quartz furnace of an atomizer, and an inner pipe of the quartz furnace is communicated with inert gas;
2, switching on a power supply of the atomic fluorescence instrument, selecting a single-channel mode or a double-channel mode on a setting page of a desktop system, confirming conditions required by testing, lighting an excitation light source of an element to be tested and preheating;
operation 3, opening valves of the carrier gas and inert gas steel cylinder, adjusting respective air pressure and flow according to setting, opening an exhaust device of the atomizer, and connecting a furnace wire power supply;
operation 4, starting the sample introduction system to finish sampling and conveying, and after the gas-liquid separator finishes reduction reaction to generate mixed gas, enabling the atomizer to ignite, and the excitation light source and the detector to work to obtain a fluorescence signal value of an element to be detected in the test solution;
operation 5, respectively measuring the fluorescence signal values of the elements to be measured in the standard series solutions, and making a fluorescence signal value-concentration standard curve; and (3) measuring the fluorescence signal value of the element to be measured in the sample solution, obtaining the concentration of the element to be measured in the sample solution from the standard curve, and calculating the content of the element to be measured in the sample after inputting the relevant parameters.
7. The method for hydride generation atomic fluorescence analysis by external tube injection according to claim 6, wherein the element to be detected is one, and the single-pass mode is set in operation 2.
8. The method for hydride generation atomic fluorescence analysis by external tube injection according to claim 6, wherein the number of the elements to be detected is two, and the operation 2 is set to a two-pass mode.
9. The method for hydride generation atomic fluorescence analysis by external tube sampling according to claim 6, wherein the standard series solution in operation 5 contains two elements, fluorescence signal values of the two elements are obtained after the same sample solution is injected, a fluorescence signal value-concentration standard curve is prepared for the two elements after the standard series solution is measured, and the concentrations of the corresponding elements to be measured in the sample solution are obtained from the two standard curves.
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| CN113418879A (en) * | 2021-06-24 | 2021-09-21 | 宁夏新龙蓝天科技股份有限公司 | Copper chloride solution detection method |
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| MY196504A (en) | 2023-04-17 |
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