High-precision measuring method for Ga content of geological sample

Abstract

The invention provides a geological sample Ga content high-precision determination method, which comprises: collecting and crushing a geological sample, weighing the crushed geological sample, and dissolving the sample; the method comprises the following steps: primarily measuring the Ga content by adopting an external standard method in combination with ICP-MS (Inductively Coupled Plasma Mass Spectrometry) to obtain primary Ga content data, and determining the addition amount of a Ga diluent according to the primary Ga content data; the method comprises the following steps: accurately weighing a geological sample and a Ga diluent, and sequentially adding the weighed geological sample and Ga diluent into a sample dissolving container for sample dissolving to obtain a dissolving solution; carrying out Ga separation and purification on the dissolved solution by adopting a cation-anion exchange method to obtain a Ga element-containing solution; and carrying out high-precision determination on the solution containing the Ga element by adopting MC-ICP-MS to obtain the Ga content. According to the method, the Ga content in the ppb-level geological sample can be accurately measured, and the Ga content measurement precision is improved.

Description

Technical Field

[0001] This invention belongs to the field of high-precision determination of Ga content, specifically relating to a high-precision method for determining the Ga content of geological samples. Background Technology

[0002] In recent years, various modern instrumental analytical techniques have been applied to the determination of gallium in geological samples. Currently, the main methods for gallium content determination include external standard method combined with spectrophotometry, atomic absorption spectroscopy, X-ray fluorescence spectroscopy (XRF), inductively coupled plasma mass spectrometry (ICP-MS), and inductively coupled plasma atomic emission spectrometry (ICP-AES). In recent years, laser ablation inductively coupled plasma mass spectrometry has also been applied to the analysis of Ga in geological samples. However, these analytical methods currently suffer from limitations such as low sensitivity, poor detection limits, and inaccurate results. Furthermore, most pretreatment processes do not incorporate targeted separation and enrichment procedures, leading to significant matrix interference and isotopic interference. Existing techniques for Ga separation and enrichment often employ three-column separation methods and require large amounts of solvent, resulting in high experimental costs. These techniques are primarily used in gallium isotope composition studies and are rarely introduced into traditional content analysis, leading to poor accuracy and precision in gallium content determination.

[0003] To address the aforementioned issues, it is necessary to propose a well-designed and effective method for high-precision determination of Ga content in geological samples. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art, and to provide a high-precision method for determining the Ga content in geological samples.

[0005] This invention provides a high-precision method for determining the Ga content in geological samples, the method comprising: Step 1: Collect and crush geological samples, and weigh the crushed geological samples for dissolution. Step 2: Use the external standard method combined with ICP-MS to perform preliminary Ga content determination, obtain preliminary Ga content data, and determine the amount of Ga diluent to be added based on the preliminary Ga content data; Step 3: Accurately weigh the geological sample and Ga diluent, and then add the weighed geological sample and Ga diluent to the dissolving container in sequence to dissolve the sample and obtain the dissolving solution; Step 4: The solution is purified by cation-anion exchange to obtain a solution containing Ga. Step 5: The Ga-containing solution is analyzed with high precision using MC-ICP-MS to obtain the Ga content.

[0006] Optionally, step four involves using a cation-anion exchange method to separate and purify Ga from the solution, including: A cation exchange resin column is provided, and the cation exchange resin column is cleaned and equilibrated. The solution was loaded into the cation exchange resin column, and 1 mL to 2 mL of 1 M HNO3 was added to the cation exchange resin column in 5 to 6 batches for elution to remove interfering elements. The cation exchange resin column was eluted with 1 mL to 2 mL of 6M HCl in 7 to 8 separate additions to obtain a solution containing Ga and other impurity elements. An anion exchange resin column is provided, and the anion exchange resin column is cleaned and equilibrated. The solution containing Ga and other impurity elements was loaded into the anion exchange resin column, and 1 mL to 2 mL of 6M HCl was added to the anion exchange resin column in 7 to 8 portions to elute the remaining impurities. The anion exchange resin column was eluted with 1 mL to 2 mL of 50% HNO3 in 5 to 6 separate additions to obtain the Ga-containing solution.

[0007] Optionally, the volume of the cation exchange resin column is 1 mL to 2 mL, and the volume of the anion exchange resin column is 1 mL to 2 mL.

[0008] Optionally, the cation exchange resin column is cleaned and equilibrated, including: Add 1 mL to 2 mL of 6M HCl to the cation exchange resin column in 5 to 6 portions to clean the resin; Add 1 mL to 2 mL of HNO3 to the cation exchange resin column in 5 to 6 separate steps to wash and equilibrate the resin.

[0009] Optionally, the anion exchange resin column is cleaned and equilibrated, including: Add 1 mL to 2 mL of 50% HNO3 to the anion exchange resin column in 5 to 6 portions to clean the resin; Add 1 mL to 2 mL of 6 M HCl to the anion exchange resin column 5 to 6 times to wash and equilibrate the resin.

[0010] Optionally, step three includes: Accurately weigh 0.01 g to 0.1 g of geological sample into a Teflon-sealed container; Use a pipette to add the weighed Ga diluent to the PFA dissolving vessel, and then use 1 mL of concentrated HNO3 to transfer the Ga diluent from the PFA dissolving vessel to a Teflon-sealed container to mix with the sample. Repeat the transfer three times, then add 1 mL of HCl to the Teflon container; After fitting a metal sleeve over a Teflon canister, place it in an oven and heat at 200℃~250℃ for 10h~12h to obtain the solution.

[0011] Optionally, after obtaining the solution, the method further includes: After the solution has cooled, transfer the solution from the Teflon container to a plastic centrifuge tube; After making up to volume with pure water, centrifuge the solution and collect the supernatant in a PFA dissolution vessel. The PFA dissolution vessel was heated to dryness on a hot plate, then HNO3 was added to redissolve it. This process was repeated twice. Finally, the solution was diluted to 2-3 mL of 1 M HNO3 solution for column loading.

[0012] Optionally, in step one, the crushed geological sample is weighed and dissolved, including: Accurately weigh 0.01 g to 0.1 g of sample into a 10 mL Teflon-sealed container; Add 1 mL of HCl and 3 mL of HNO3 to a Teflon-sealed container; After fitting the Teflon can with a metal sleeve, place it in an oven and heat at 200℃~250℃ for 10 h~12 h.

[0013] Optionally, after weighing and dissolving the crushed geological sample, the method further includes: After the solution has cooled, transfer the solution from the Teflon container to a plastic centrifuge tube; After making up to volume with ultrapure water, centrifuge the solution and collect the supernatant in a PFA dissolution vessel. Place the PFA sample dissolution vessel on a hot plate and heat it to dryness. Then add HNO3 to redissolve it. Repeat this process twice. Finally, dilute the solution to 2 mL ~ 5 mL of 2% ~ 5% HNO3 solution for instrument testing.

[0014] Optionally, step five includes: Establish the cup structure for static determination of Ga isotopes; Ga isotope determination was performed by MC-ICP-MS based on the described cup structure; The Ga content is obtained based on the measured Ga isotopes.

[0015] The high-precision method for determining Ga content in geological samples of the present invention combines a multi-receiver inductively coupled plasma mass spectrometer (MC-ICP-MS) with isotope dilution method to measure Ga content. At the same time, a targeted and simplified Ga separation and enrichment process is introduced in the pretreatment process, which can accurately determine the Ga content in geological samples at the ppb level, thereby improving the accuracy of Ga content determination. Attached Figure Description

[0016] Figure 1 This is a schematic flowchart of a method for high-precision determination of Ga content in geological samples according to an embodiment of the present invention.

[0017] Figure 2 This is a schematic diagram showing the relationship between isotope ratio and error amplification factor, provided for another embodiment of the present invention. Detailed Implementation

[0018] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0019] like Figure 1 As shown, the present invention provides a high-precision method S100 for determining the Ga content in geological samples, the method S100 comprising: Step 1: Collect and crush geological samples, and weigh the crushed geological samples for dissolution.

[0020] Specifically, geological samples are collected and crushed to approximately 200 mesh. The specific process for weighing and dissolving the crushed geological samples is as follows: First, accurately weigh 0.01 g to 0.1 g of the sample into a 10 mL Teflon-sealed container. Specifically, use a Class I balance (d=0.01 mg / 0.1 mg, max=42 g / 152 g) to accurately weigh 0.01 g to 0.1 g of the sample into a 10 mL Teflon-sealed container.

[0021] Next, add 1 mL of HCl (analytical grade) and 3 mL of HNO3 (analytical grade) to the Teflon-sealed container.

[0022] Next, after fitting the Teflon can with a metal sleeve, place it in an oven at 200℃~250℃ for 10 h~12 h to dissolve the sample. Specifically, in this embodiment, it is placed in an oven at 200℃ for 12 h.

[0023] In this embodiment, aqua regia containing 1 mL of HCl (superior grade) and 3 mL of HNO3 (superior grade) is used for sample dissolution. Its strong oxidizing properties can destroy the crystal lattice or organic matter of the insoluble sample, making it easier to dissolve the insoluble geological sample.

[0024] The method further includes, after weighing and dissolving the crushed geological sample, the following steps: First, after the solution has cooled, transfer it from the Teflon container to a plastic centrifuge tube. Specifically, after the solution has cooled, transfer it from the Teflon container to a 15mL plastic centrifuge tube.

[0025] Next, after bringing the volume down with ultrapure water, centrifuge the sample and collect the supernatant in a PFA dissolution vessel. Specifically, bring the volume down to 10 mL with ultrapure water and centrifuge at 2000 rpm for 10 min.

[0026] Next, place the PFA dissolution vessel on a hot plate and heat it to dryness. Then, add HNO3 to redissolve it. Repeat this process twice. Finally, dilute the solution to 2 mL to 5 mL of 2% to 5% HNO3 solution for instrument testing.

[0027] Specifically, take 0.5 mL of supernatant into a 15 mL PFA dissolution vessel, heat it to dryness on a 150℃ hot plate, then redissolve it with nitric acid, repeat twice, and finally dilute the solution to 2 mL ~ 5 mL of 2% ~ 5% nitric acid solution for instrument testing.

[0028] In this embodiment, the dissolved sample is centrifuged to prevent invisible fine particles from clogging the injector during the instrumentation process. At the same time, nitric acid is added multiple times to redissolve the sample in order to remove HCl and prevent its chloride ions from interfering with and damaging the instrument.

[0029] Step 2: Use the external standard method combined with ICP-MS to perform preliminary Ga content determination, obtain preliminary Ga content data, and determine the amount of Ga diluent to be added based on the preliminary Ga content data.

[0030] Specifically, ICP-MS was used to directly test the solution after volume adjustment to quickly obtain the preliminary Ga isotope ratio. Then, the initial Ga content data was calculated based on the Ga isotope ratio, and the amount of Ga diluent to be added was determined based on the preliminary Ga content data.

[0031] The Ga content is calculated based on the measured Ga isotope ratios using the following formula: ; Table 1. Meaning and values ​​of each variable in Equation 1-1

[0032] Differentiating from equation (1-1) yields: ; Equations 1-2 express the error propagation in calculating the content from the isotope ratio. It can be seen from the above equation that the magnitude of the isotope ratio R after mixing directly affects the error amplification of the dilution method. Let the amplification factor be: ; Based on the above formula, the amplification factor Fmag is relative to the isotope ratio R. Figure 2 As shown, Figure 2This visually illustrates the relationship between the magnification factor and the isotopic ratio after mixing the sample and diluent. For Ga... 69 Ga / 71 The Ga ratio variation has a ratio corresponding to the minimum amplification factor. To obtain the isotope ratio at the optimal dilution, let the first derivative of equation 1-3... This allows us to determine the A / B isotope ratio R at the minimum amplification factor, i.e., the optimal dilution. opt： ; The calculation based on the above formula yields the result when Ga is measured. 69 Ga / 71 The optimal dilution ratio for Ga is 0.06, which minimizes error amplification. However, considering that the optimal measurement ratio for ICP-MS should be 1, a compromise is adopted in practical analysis. The selected isotope ratio dilution ratio for Ga is 0.3, therefore the ideal mass ratio of diluent to sample (i.e., amount of diluent added / amount of analyte in the sample) for Ga is 1.6, as shown in the last row of Table 1-1. The amount of diluent added should ideally be close to this mass ratio; too high or too low a ratio will result in excessive errors in the measurement of element content and isotope ratios.

[0033] In this embodiment, the Ga content is initially determined by using the external standard method combined with ICP-MS to obtain preliminary Ga content data. Based on the preliminary Ga content data, the amount of Ga diluent to be added is determined, which can yield more accurate content results.

[0034] Step 3: Accurately weigh the geological sample and Ga diluent, and then add the weighed geological sample and Ga diluent to the dissolving container in sequence to dissolve the sample and obtain the dissolving solution.

[0035] The specific process of step three can be as follows: First, accurately weigh 0.01 g to 0.1 g of geological sample into a Teflon-sealed container. Specifically, use a Class I balance (d=0.01mg / 0.1mg, max=42g / 152g) to accurately weigh 0.01 g to 0.1 g of sample into a 10 mL Teflon-sealed container (depending on the Ga content in the sample, ensure the concentration on the balance is greater than several tens of ng / g).

[0036] Next, use a pipette to add the weighed Ga diluent to the PFA dissolving vessel, and then use 1 mL of concentrated HNO3 to transfer the Ga diluent from the PFA dissolving vessel to a Teflon-sealed container to mix with the sample.

[0037] Specifically, use a pipette to transfer and accurately weigh an appropriate amount using a balance. 71Place the Ga diluent into the corresponding 15 mL PFA dissolution vessel, and then use 1 mL of concentrated HNO3 (analytical grade) to transfer the diluent from the PFA dissolution vessel into the corresponding Teflon-sealed container to mix with the sample.

[0038] Next, repeat the transfer three times, then add 1 mL of HCl to the Teflon-sealed container. Specifically, repeat the transfer three times (adding 3 mL of HNO3 to the container), then add 1 mL of HCl (analytical grade) to the Teflon-sealed container. The 3 mL of HNO3 and 1 mL of HCl form a reverse aqua regia combination, which better dissolves the sample.

[0039] Finally, the Teflon can is fitted with a metal sleeve and placed in an oven at 200℃~250℃ for 10h~12h to obtain the solution. Specifically, the Teflon can is fitted with a metal sleeve and placed in an oven at 200℃ for 12h to dissolve the sample.

[0040] In this embodiment, directly adding the diluent to the sealed container containing the sample would cause the nitric acid medium in the diluent to react directly with the sample, potentially even generating bubbles. During this process, it is impossible to accurately weigh the diluent. Therefore, the diluent must be weighed in advance into its corresponding container and then transferred to the sealed container with HNO3 to mix with the sample, thus improving the accuracy of the diluent weighing. Furthermore, adding the diluent before dissolving the sample and heating it for an extended period helps ensure uniform mixing of the sample and diluent, achieving isotopic equilibrium. Even if some sample is lost during the dissolution process or subsequent experiments, it will not affect the analytical results, improving the measurement structure.

[0041] After obtaining the solution, the method further includes: First, after the solution has cooled, transfer the solution from the Teflon container to a plastic centrifuge tube. Specifically, after the solution has cooled, transfer the solution and insoluble matter from the Teflon container to a 15 mL plastic centrifuge tube.

[0042] Next, after bringing the volume down with pure water, centrifuge the sample and collect the supernatant in a PFA dissolving vessel. Specifically, bring the volume down to 5 mL with ultrapure water, centrifuge at 2000 rpm for 10 min, and collect all the supernatant in a 15 mL PFA dissolving vessel.

[0043] Finally, the PFA dissolution vessel was placed on a hot plate and heated to dryness, then HNO3 was added to redissolve it. This process was repeated twice. Finally, the solution was diluted to 2 mL to 3 mL of 1 M HNO3 solution for column loading.

[0044] Specifically, the PFA dissolution vessel is heated to dryness on a 150°C hot plate, then HNO3 is added to redissolve it, and this process is repeated twice. Finally, the solution is diluted to 2 mL~3 mL of 1 M HNO3 solution for column loading.

[0045] In this embodiment, adding HNO3 to redissolve the solution multiple times can convert the solution into a nitric acid medium, which is helpful for subsequent column chromatography experiments. Before each redissolution, the solution should be evaporated to ensure that the hydrochloric acid is removed.

[0046] Step 4: The solution is purified by cation-anion exchange to obtain a solution containing Ga.

[0047] 1) Provide a cation exchange resin column, and clean and equilibrate the cation exchange resin column. The volume of the cation exchange resin column is 1 mL to 2 mL.

[0048] The cleaning and column equilibration of the cation exchange resin column include: Add 1 mL to 2 mL of 6M HCl to the cation exchange resin column 5 to 6 times to clean the resin; add 1 mL to 2 mL of HNO3 to the cation exchange resin column 5 to 6 times to clean and equilibrate the resin.

[0049] 2) Load the solution into the cation exchange resin column, and add 1 mL to 2 mL of 1M HNO3 into the cation exchange resin column in 5 to 6 batches for elution to remove interfering elements.

[0050] 3) Add 1 mL to 2 mL of 6M HCl to the cation exchange resin column 7 to 8 times for filtration and extraction to obtain a solution containing Ga and other impurity elements.

[0051] 4) Provide an anion exchange resin column, and clean and equilibrate the anion exchange resin column. The volume of the anion exchange resin column is 1 mL to 2 mL.

[0052] The anion exchange resin column is cleaned and equilibrated, including: Add 1 mL to 2 mL of 50% HNO3 to the anion exchange resin column 5 to 6 times to clean the resin; add 1 mL to 2 mL of 6 M HCl to the anion exchange resin column 5 to 6 times to clean and equilibrate the resin.

[0053] 5) Load the solution containing Ga and other impurity elements into the anion exchange resin column, and add 1 mL to 2 mL of 6M HCl into the anion exchange resin column in 7 to 8 portions to elute the remaining impurities.

[0054] 6) Add 1 mL to 2 mL of 50% HNO3 to the anion exchange resin column 5 to 6 times for filtration and extraction to obtain the Ga-containing solution.

[0055] As shown in Table 2, in this embodiment, the process of separating and purifying Ga using cation exchange resin columns and anion exchange resin columns is as follows: 1) Prepare an AG-50-8X (200-400 mesh) cation exchange column with a column volume of about 1 mL. First, add 1 mL of 6 M HCl (total 5 mL) in 5 portions to wash the resin. Then, add 1 mL of 1 M HNO3 (total 5 mL) in 5 portions to wash and equilibrate the resin.

[0056] Adding the solution in small, multiple batches can maximize the adsorption / complexation efficiency between the target element and the stationary phase (resin), while reducing matrix interference and target element loss. 2) Add 2 mL of the prepared 1 M HNO3 solution to the cation exchange column to coat Ga onto the resin. Then, add 1 mL of 1 M HNO3 in 5 portions (total 5 mL) to elute interfering elements such as Ge. 3) Add 1 mL of 6 M HCl in 7 portions (total 7 mL) to collect Ga and other impurity elements. 4) Prepare an AG-1-8X (200-400 mesh) anion exchange column with a column volume of about 1 mL. First, add 1 mL of 50% HNO3 (total 5 mL) in 5 portions to wash the resin. Then, add 1 mL of 6 M HCl (total 5 mL) in 5 portions to wash and equilibrate the resin.

[0057] 5) Add 1 mL of 6 M HCl in 7 portions (total 7 mL) to elute impurity elements.

[0058] 6) Add 1 mL of 50% HNO3 in 5 portions (total 5 mL) to collect Ga element. Transfer the collected solution to a 15 mL PFA dissolution vessel, evaporate to dryness twice on a 150℃ hot plate, and then dissolve in 3 mL of 2~5% HNO3 solution for instrument testing.

[0059] In this embodiment, adding the eluent in small amounts multiple times maximizes the adsorption / complexation efficiency between the target element and the resin, reduces matrix interference and target element loss, and improves the separation effect of Ga. Furthermore, in this embodiment, only two resin columns are needed to separate and enrich Ga, reducing costs; additionally, the volume of both resin and eluent is small, eliminating the need for large amounts of solvent to separate Ga, further reducing costs.

[0060] Table 2. Process of separating and purifying Ga from the solution using cation-anion exchange method.

[0061] Step 5: The Ga-containing solution is analyzed with high precision using MC-ICP-MS to obtain the Ga content.

[0062] Specifically, step five may include: Establish a cup structure for static determination of Ga isotopes; perform MC-ICP-MS determination of Ga isotopes based on the cup structure; and obtain the Ga content based on the measured Ga isotopes.

[0063] Specifically, Ga content was analyzed directly using a Neptune Plus MC-ICP-MS manufactured by Thermo Fisher Scientific. The multi-receiver inductively coupled plasma mass spectrometer at the Re-Os Key Laboratory of the National Geological Experiment and Testing Center employed both energy and mass focusing modes. Equipped with dynamic zoom technology, it improved ion mass dispersion by 17%. It featured seven Faraday cup receivers and a fixed central channel ion counter receiver. In addition to the central cup, four electric motors on each side (high and low mass number) were used for precise positional adjustments. An electron multiplier was located behind the central cup, and four ion counters were positioned outside the lowest mass number cup. This system enabled simultaneous static Faraday cup measurement and quasi-static measurement with single-peak jumping of the ion counters. The use of a high-sensitivity JET sampling cone and X-shaped truncation cone significantly improved sensitivity by approximately two times, achieving an internal measurement accuracy of less than 0.05%. For Ga, simultaneous determination was performed using static Faraday mode. 69 Ga and 71 Ga was corrected using a Ga standard solution as an external standard.

[0064] Finally, the Ga content in the sample was calculated using the isotope dilution method. The specific calculation process can be found in Formula 1-1 used for the initial Ga content determination, and will not be repeated here.

[0065] The high-precision method for determining Ga content in geological samples of the present invention combines a multi-receiver inductively coupled plasma mass spectrometer (MC-ICP-MS) with isotope dilution method to measure Ga content. At the same time, a targeted and simplified Ga separation and enrichment process is introduced in the pretreatment process, which can accurately determine the Ga content in geological samples at the level of tens of ppb, thereby improving the accuracy of Ga content determination.

[0066] The high-precision method for determining Ga content in geological samples according to the present invention was used to analyze standard substances GBW07270, GBW07128, and GBW07107. The analysis results are as follows: The experimental procedure is blank as follows: Table 3 Experimental Procedure Data

[0067] The detection limit of Ga in this experiment can be calculated from Table 3. The limit is 0.01 ppb, which is the three-times standard deviation of six consecutive determinations of the blank in the whole process.

[0068] Table 4 shows the Ga content data determined by the high-precision method for determining Ga content in geological samples according to the present invention. As can be seen from Table 4, the pg-level detection limit can be used to determine ng-level samples well (GBW07128, accuracy of about 2%), and can be used to determine ug-level samples more accurately (GBW07270, accuracy of less than 1%).

[0069] Table 4 Ga content determination data

[0070] Table 5 shows the detection limit data for Ga content determination using mainstream analytical methods such as ICP-MS. As can be seen from Table 5, the detection limit data for Ga content are all worse than the detection limit data obtained by the method of this invention.

[0071] Table 5. Detection limits of Ga methods in different existing literature

[0072] Meanwhile, Ga elemental analysis mainly focused on samples at the ppm level, with very few Ga content analyses at the ppb level, as shown in Table 6: Table 6. Precision and accuracy of Ga methods in different existing literature

[0073] In summary, the detection limit of Ga content in geological samples determined by the high-precision method of the present invention (0.01 ppb) is significantly lower than the detection limit of current mainstream analytical methods (60 ppb ~ 2000 ppb), and can handle the analysis and testing of samples at the ppb level.

[0074] It is understood that the above embodiments are merely exemplary implementations used to illustrate the principles of the present invention, and the present invention is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.

Claims

1. A method for high-precision determination of the content of gallium in geological samples, characterized in that, The method comprises: Step one, collecting and crushing geological samples, and weighing the crushed geological samples for sample dissolution; Step two, performing initial Ga content measurement by external standard method combined with ICP-MS to obtain preliminary Ga content data, and determining the addition amount of Ga diluent according to the preliminary Ga content data; Step three, accurately weighing the geological samples and the Ga diluent, and sequentially adding the weighed geological samples and the Ga diluent into a sample dissolution container for sample dissolution to obtain a dissolution solution; Step four, performing Ga separation and purification on the dissolution solution by cation-anion exchange method to obtain a Ga element-containing solution; Step five, performing high-precision measurement on the Ga element-containing solution by MC-ICP-MS to obtain Ga content.

2. The method of claim 1, wherein, In step four, the Ga separation and purification on the dissolution solution by cation-anion exchange method comprises: providing a cation resin column and cleaning and column equilibrating the cation resin column; loading the dissolution solution into the cation resin column, adding 1 mL to 2 mL of 1M HNO3 into the cation resin column in 5 to 6 times for leaching and elution to elute interfering elements; continuing to add 1 mL to 2 mL of 6M HCl into the cation resin column in 7 to 8 times for leaching and elution to obtain a Ga element-containing solution and remaining impurity element solution; providing an anion resin column and cleaning and column equilibrating the anion resin column; loading the Ga element-containing solution and remaining impurity element solution into the anion resin column, adding 1 mL to 2 mL of 6M HCl into the anion resin column in 7 to 8 times to elute the remaining impurities; continuing to add 1 mL to 2 mL of 50% HNO3 into the anion resin column in 5 to 6 times for leaching and elution to obtain the Ga element-containing solution.

3. The method of claim 2, wherein, The volume of the cation resin column is 1 mL to 2 mL, and the volume of the anion resin column is 1 mL to 2 mL.

4. The method of claim 2, wherein, The cleaning and column equilibrating of the cation resin column comprises: adding 1 mL to 2 mL of 6M HCl into the cation resin column in 5 to 6 times for cleaning the resin; adding 1 mL to 2 mL of HNO3 into the cation resin column in 5 to 6 times for cleaning and equilibrating the resin.

5. The method of claim 2, wherein, The cleaning and column equilibrating of the anion resin column comprises: adding 1 mL to 2 mL of 50% HNO3 into the anion resin column in 5 to 6 times for cleaning the resin; adding 1 mL to 2 mL of 6M HCl into the anion resin column in 5 to 6 times for cleaning and equilibrating the resin.

6. The method according to any one of claims 1 to 5, characterized in that, Step three comprises: accurately weighing 0.01 g to 0.1 g of geological samples in a Teflon bomb; adding the weighed Ga diluent into a PFA sample dissolution tank with a pipette, and then transferring the Ga diluent in the PFA sample dissolution tank into the Teflon bomb to mix with the sample by using 1 mL of concentrated HNO3; after repeating the transfer for 3 times, adding 1 mL of HCl into the Teflon bomb; after covering the Teflon bomb with a metal sleeve, placing it into an oven for heating at 200°C to 250°C for 10 h to 12 h to obtain the dissolution solution.

7. The method of claim 6, wherein, After obtaining the dissolving solution, the method further comprises: After the dissolving solution is cooled, the dissolving solution in the Teflon jar is transferred to a plastic centrifuge tube; After constant volume with pure water, centrifugation is performed with a centrifuge, and the supernatant is taken to a PFA dissolving tank; The PFA dissolving tank is placed on an electric heating plate for heating and evaporation, and then HNO3 is added for redissolution, which is repeated twice, finally the dissolving solution is constant volume in 2 mL~3 mL 1 M HNO3 solution for column loading.

8. The method according to any one of claims 1 to 5, characterized in that, In step one, the broken geological sample is weighed for dissolving, comprising: 0.01 g~0.1 g sample is accurately weighed in a 10 mL Teflon jar; 1 mL HCl and 3 mL HNO3 are added to the Teflon jar; After the Teflon jar is sleeved with a metal sleeve, it is placed in an oven at 200℃~250℃ for heating for 10 h~12 h.

9. The method of claim 8, wherein, After the broken geological sample is weighed for dissolving, the method further comprises: After the solution is cooled, the solution in the Teflon jar is transferred to a plastic centrifuge tube; After constant volume with ultrapure water, centrifugation is performed with a centrifuge, and the supernatant is taken to a PFA dissolving tank; The PFA dissolving tank is placed on an electric heating plate for heating and evaporation, and then HNO3 is added for redissolution, which is repeated twice, finally the solution is constant volume in 2 mL~5 mL 2%~5% HNO3 solution for machine testing.

10. The method according to any one of claims 1 to 5, characterized in that, In step five, comprising: A cup structure for static determination of Ga isotopes is established; Ga isotopes are determined by MC-ICP-MS according to the cup structure; Ga content is obtained according to the determined Ga isotopes.

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