A method for separation, purification and detection of copper isotopes in geological samples

Abstract

The invention discloses a separation, purification and detection method of copper isotopes in geological samples, the separation and purification method comprising: extracting a digestion solution of a geological sample by a double column method; in the double column used, the first column is filled with 1 ml of 200-400 mesh AG1-X8 resin or 2 ml of 100-200 mesh AG MP-1M resin, and the second column is filled with 1 ml of 100-200 mesh AG MP-1M resin; the first elution treatment performed by the first column and the second elution treatment performed by the second column are both eluents of hydrochloric acid. The separation and purification method of the invention can improve the separation recovery rate of copper, improve the detection accuracy, and reduce the acid dosage and cost at the same time.

Description

Technical Field

[0001] The invention relates to the technical field of methods for detecting copper isotopes in geological samples. Background Art

[0002] Isotopes are atoms with the same number of protons and different numbers of neutrons, occupying the same position in the periodic table, such as the three main isotopes of carbon. 12 C. 13 C. 14 C has 6 protons, but the number of neutrons is 6, 7, and 8 respectively. Stable isotopes are atoms of the same element with relatively stable physical properties and no radioactivity or radiation effects. There are more than 300 of them. The opposite is unstable isotopes or radioactive isotopes. Taking carbon isotopes as an example, 12 C. 13 C is a stable isotope, and 14 C is a radioactive isotope.

[0003] Stable isotopes are non-radioactive, safe, accurate, and do not interfere with nature. They have the ability to integrate long-term geochemical changes and connect components of different systems, playing a unique role as a liaison in time and space. Their analysis technology can be used in geochemistry, tracing and tracing. Today, isotope composition determination technology is widely used in geochemistry, geology, space science, nuclear science, archaeology, biology and other fields. Thermal ionization mass spectrometry (TIMS) with a hot surface ionization ion source is an early isotope determination technology, mainly used for solid isotope analysis. Since the 1990s, the application of multi-receiver inductively coupled plasma mass spectrometers (MC-ICP-MS) has enabled the rapid development of high-precision determination methods for metal stable isotopes. In comparison, MC-ICP-MS has the advantages of fast analysis speed, high sensitivity, and the ability of the ICP ion source to ionize metal elements and some non-metallic elements.

[0004] The key to MC-ICP-MS isotope analysis is to separate and purify the samples to meet the analytical requirements. Pretreatment mainly includes sample digestion and separation and purification of the elements to be measured. Two requirements usually need to be met during the treatment process: (1) try not to introduce elements that may cause interference, that is, the background generated by the treatment should be reduced to the lowest level; (2) try not to lose the elements to be measured, that is, the recovery rate should be as high as possible to 100%.

[0005] To meet the above requirements, the prior art has developed ion exchange chromatography, which is to fill the resin column with ion exchange resin, and exchange the free metal ions with the ions bound to the active groups in the resin according to the different affinities between different ions in the sample and the active groups of the resin, so as to achieve the separation purpose. According to the number of column passes, the existing methods for separating and purifying copper in geological samples by ion exchange chromatography can be divided into single column method, double column method and triple column method. Among them, the common single column method is as follows: by 2ml AG MP-1M resin is used to separate and purify copper from igneous rocks (copper content ~ 0.4 μg), and the following eluents are used in sequence: 8 ml of 8M HCl, 1 ml of 8M HCl and 0.001wt% H2O2, 10 ml of 8M HCl and 24 ml of 8M HCl and 0.001wt% H2O2; double column method: 0.5 ml of Cu-Selective resin and 0.5 ml of AG50W-X12 resin are used to separate and purify copper from igneous rocks (copper content ~ 0.4 μg). The copper element of the stone sample was separated and purified using the following eluents in sequence: 4 ml of 0.001M HNO3, 2 ml of 0.001M HNO3, 4 ml of 0.001M HNO3, 6 ml of 0.5M HNO3 and 3 ml of 0.5M HNO3, as well as 6 ml of 0.5M HNO3, 4 ml of 0.5M HNO3 and 0.1M HF, 4 ml of 0.5M HNO3 and 1wt% H2O2, 5 ml of 2M HNO3, etc. The above methods often have one or more of the following defects: (1) The amount of acid used in the whole process is large, which is costly; (2) It is difficult to effectively separate the matrix elements in the low copper content sample, and it is necessary to repeatedly pass through the column, which increases the separation and purification cost; (3) The resin is expensive. If it is not reused, the separation and purification cost will be significantly increased. If it is reused, the separated Cu will contain a higher content of matrix elements due to the memory effect, affecting the detection accuracy; (4) There is still a certain proportion of other metal elements that have not been removed in the eluent after passing through the column, which affects the detection accuracy. Summary of the invention

[0006] In view of the defects of the prior art, the purpose of the present invention is to propose a new separation, purification and detection method for copper isotopes in geological samples. The separation and purification method can reduce the amount of acid used in the whole process, reduce the blank of the whole process, efficiently separate the copper element from other matrix elements in the sample, obtain a high-purity separation product, and improve the accuracy of subsequent copper isotope detection by MC-ICP-MS. At the same time, the resin used in the method is economical and has low overall cost.

[0007] The technical solution of the present invention is as follows:

[0008] A method for separating and purifying copper isotopes in geological samples, comprising:

[0009] Digestion treatment is performed on geological samples containing copper to obtain a basic treatment solution;

[0010] Performing a first pre-elution treatment on the first column, and performing a first elution treatment on the basic treatment liquid through the first column that has completed the first pre-elution treatment;

[0011] The copper separation liquid obtained by the first elution treatment is heated and evaporated to dryness, and the volume is fixed with 8M HCl solution to obtain a first column treatment liquid;

[0012] performing a second pre-elution treatment on the second column, and performing a second elution treatment on the first column treated liquid through the second column that has completed the second pre-elution treatment to obtain a copper recovery liquid;

[0013] The first column is filled with 1 ml of 200-400 mesh AG1-X8 resin or 2 ml of 100-200 mesh AG MP-1M resin, and the second column is filled with 1 ml of 100-200 mesh AG MP-1M resin; the eluents used in the first elution treatment and the second elution treatment are both hydrochloric acid.

[0014] According to some preferred embodiments of the present invention, the first column is filled with 1 ml of AG1-X8 resin with a mesh size of 200-400, and the first elution treatment comprises eluting with the following eluents in sequence: 2 ml of 6M hydrochloric acid, 1 ml of 6M hydrochloric acid, 4 ml of 6M hydrochloric acid and 4 ml of 0.4M hydrochloric acid, and the effluent obtained when 4 ml of 0.4M hydrochloric acid is used as the eluent is collected, i.e., the copper separation solution.

[0015] According to some preferred embodiments of the present invention, the first column is filled with 2 ml of 100-200 mesh AG MP-1M resin, and the first elution treatment comprises eluting with the following eluents in sequence: 4 ml of 8 M hydrochloric acid, 1 ml of 8 M hydrochloric acid, 9 ml of 8 M hydrochloric acid and 6 ml of 0.4 M hydrochloric acid, and the effluent obtained when 6 ml of 0.4 M hydrochloric acid is used as the eluent is collected, i.e., the copper separation solution.

[0016] According to some preferred embodiments of the present invention, the second elution treatment comprises eluting with the following eluents in sequence: 2 ml of 8M hydrochloric acid, 1 ml of 8M hydrochloric acid, 4 ml of 8M hydrochloric acid and 10 ml of 8M hydrochloric acid, and collecting the effluent obtained when 10 ml of 8M hydrochloric acid is used as the eluent, i.e., the copper recovery liquid.

[0017] According to some preferred embodiments of the present invention, the digestion process comprises:

[0018] (1) Weigh less than 30 mg of geological sample powder;

[0019] (2) 1 ml of 15.8 M HNO3 and 0.5 ml of 23.1 M HF are added to the geological sample powder in sequence, and the mixture is sealed and heated at 150-160°C for 25-35 min, followed by ultrasonic treatment, and then the heating and ultrasonic treatment are performed alternately until the geological sample is completely dissolved or a small amount of insoluble white flocculent precipitate is present;

[0020] (3) evaporating the solution obtained in step (2) at 150-160° C. to dryness, and cooling to room temperature;

[0021] (4) adding 0.5 ml of 15.8 M HNO3 and 1.5 ml of 10.1 M HCl to the evaporated product obtained in step (3), sealing the mixture and heating it at 70-90° C. until a clear solution is obtained;

[0022] (5) after the clarified solution obtained in step (4) has cooled to room temperature, evaporating to dryness at 70-90° C. in an open state;

[0023] (6) adding 1 ml of 10.1 M HCl to the evaporated product obtained in step (5), sealing the container and heating at 120-140° C. to obtain a clear solution;

[0024] (7) evaporating the clear solution obtained in step (6) at 120-140° C. to dryness, and cooling to room temperature;

[0025] (8) Add 6M HCl to the evaporated product obtained in step (7) to obtain the basic treatment solution.

[0026] According to some preferred embodiments of the present invention, the first pre-elution treatment comprises: eluting the first column with the following eluents in sequence: 10 ml of high-purity water, 5 ml of 6M hydrochloric acid and 5 ml of high-purity water.

[0027] According to some preferred embodiments of the present invention, the second pre-elution treatment comprises: eluting the second column with the following eluents in sequence: 10 ml of high-purity water, 5 ml of 8M hydrochloric acid and 5 ml of high-purity water.

[0028] The present invention also provides a method for detecting copper isotopes in geological samples, which comprises: obtaining the copper separation liquid by the above separation and purification method, and then measuring the copper isotope ratio in the copper separation liquid by MC-ICP-MS.

[0029] According to some preferred embodiments of the present invention, the determination uses an internal standard method.

[0030] The present invention has the following beneficial effects:

[0031] The present invention can further reduce the amount of acid used while better removing the matrix elements in the sample, and reduce the blank of the whole process (~2ng); the separation recovery rate of copper in the sample can be close to 100%, and low-content geological samples (such as BCR-2, Cu content: 19ppm) can be completely separated and purified without repeated column passing; the separation and purification process of copper (including the heating and evaporation process of the copper separation liquid) can be completed within 12 hours, which is simpler and more time-saving than the existing separation and purification process; compared with the method of using special-effect resin, it is more economical and practical. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The figure is a flow chart of the double column method used in Example 1 for separating and purifying copper in geological samples.

[0033] Figure 2 This is the elution curve of BHVO-2 using AG1-X8 resin in Example 1.

[0034] Figure 3 This is the elution curve of the copper separation solution using AG MP-1M resin in Example 1.

[0035] Figure 4 This is a flow chart of the double-column method used in Example 2 for separating and purifying copper elements in geological samples. DETAILED DESCRIPTION

[0036] The present invention is described in detail below in conjunction with the embodiments and drawings, but it should be understood that the embodiments and drawings are only used to exemplify the present invention and do not constitute any limitation on the protection scope of the present invention. All reasonable changes and combinations within the scope of the inventive concept of the present invention fall within the protection scope of the present invention.

[0037] The basic treatment solution used for column treatment in the following embodiments is obtained by the following steps:

[0038] (1) Accurately weigh less than 30 mg of powdered geological sample containing at least 0.4 μg of copper into a PFA sample bottle. The weighing error should be less than 5%;

[0039] (2) First add 1 ml of 15.8 M HNO3 to the PFA dissolution bottle, then add 0.5 ml of 23.1 M HF, tighten the bottle cap to ensure airtightness, and then heat it on a 160°C hot plate for 30 min, then immediately sonicate for 30 min, and then alternately heat and sonicate to accelerate dissolution;

[0040] (3) After the solution is completely dissolved (there may be some white flocculent precipitate), adjust the temperature of the electric heating plate to 150-160℃ and evaporate to dryness with the lid open;

[0041] (4) After evaporation, take out the PFA sample bottle and cool it to room temperature, then add 0.5 ml 15.8 M HNO3 and 1.5 ml 10.1 M HCl, then cover it tightly and heat it on a hot plate at 80 °C;

[0042] (5) After the sample is dissolved (clear solution), place it on a hot plate at 80°C with the lid open and evaporate to dryness;

[0043] (6) After evaporation, take out the PFA sample bottle and cool it to room temperature. Then add 1 ml of 10.1 M HCl, cover it tightly, and heat it on a hot plate at 130 °C.

[0044] (7) After the sample is dissolved (clear solution), place it on a hot plate at 130°C and evaporate to dryness with the lid open;

[0045] (8) After evaporation, take out the PFA sample bottle and cool it to room temperature. Then add 6M HCl to make the volume to 1 ml to obtain the basic treatment solution, which is then passed through the column.

[0046] Example 1

[0047] See attached Figure 1 , the double column method is used to treat the basic treatment liquid through the column, and the treatment process includes:

[0048] The first column was filled with 200-400 mesh AG1-X8 resin, the inner diameter of the first column was 0.8 cm, the height was 2 cm, that is, the filling size was 0.8 cm × 2 cm, and a total of 1 ml of AG1-X8 resin was filled; after filling, 10 ml of high-purity water (MQ water, resistivity ≥ 18.2 MΩ) and 5 ml of 6 M HCl solution were used to elute the resin in sequence, and then 5 ml of MQ water was used to adjust the resin and remove bubbles to complete the preparation before elution, and then the basic treatment liquid was subjected to the first elution treatment according to the elution process shown in Table 1, and the effluent corresponding to the final eluent was collected to obtain a copper separation liquid, and the copper separation liquid was heated at 130° C. for 2 h to evaporate to dryness, and an 8 M HCl solution was added to the obtained powder substance to make the volume 1 ml to obtain a column treatment liquid;

[0049] The second column was filled with 100-200 mesh AG MP-1M resin, the inner diameter of the second column was 0.4 cm, and the height was 8 cm, that is, the filling size was 0.4 cm×8 cm, and a total of 1 ml of AG MP-1M resin was filled; after filling, 10 ml of MQ water and 5 ml of 8 M HCl solution were used to elute the resin in sequence, and then 5 ml of MQ water was used to adjust the resin and remove bubbles to complete the preparation before elution, and then a column of treated liquid was subjected to a second elution treatment according to the elution process shown in Table 1, and the effluent corresponding to the final eluate was collected to obtain a copper recovery liquid.

[0050] Table 1 Elution process of the double column method used in Example 1

[0051]

[0052] The geological sample used in Example 1 is USGS basalt standard sample BHVO-2, and a total of 28 ml of eluent is used. The first column treatment can initially separate and purify the copper in the sample, and finally only 4 ml of 0.4M HCl is needed to elute and separate the copper and iron, and most of the matrix elements are separated and removed under the premise of ensuring the recovery rate. The second column treatment can separate the copper and iron in the column treatment liquid and remove the residual matrix elements again. Figure 2 , 3 shown.

[0053] Compared with other copper separation methods using strong alkaline anion exchange resins in the prior art, this two-column separation method can save relatively acid while removing matrix elements (including titanium, magnesium, barium, etc.) twice, and reduce the blank of the whole process, and has better economic applicability.

[0054] This embodiment uses a total of 28 ml of eluent. Through the detection of the elemental composition of the geological sample copper recovery liquid, it is found that the copper recovery liquid obtained in this embodiment has Na / Cu<0.05, Mg / Cu<0.03, Al / Cu<0.1, Ti / Cu<0.03, Fe, Ca, Ni, Cr, and Ba contents are all lower than 1ppb, and the presence of the above elements does not affect the subsequent determination, and the whole process does not introduce any elements that may interfere. The copper recovery rate of the first elution treatment is 99.93%, the copper recovery rate of the second elution treatment is 99.83%, and the full process recovery rate is 99.93%×99.83%=99.76%, which is close to 100%.

[0055] Example 2

[0056] See attached Figure 4 , the double column method is used to treat the basic treatment liquid through the column, and the treatment process includes:

[0057] The first column was filled with 100-200 mesh AG MP-1M resin, the inner diameter of the first column was 0.8 cm, the height was 4 cm, that is, the filling size was 0.8 cm×4 cm, and a total of 2 ml of AG MP-1M resin was filled; after filling, the resin was eluted with 10 ml of MQ water and 5 ml of 8M HCl solution in sequence, and then the resin was adjusted and the bubbles were removed by 5 ml of MQ water to complete the preparation before elution, and then the treatment liquid was subjected to the first elution treatment according to the elution process shown in Table 2, and the final eluate was collected to obtain a copper separation liquid, and the copper separation liquid was heated at 130° C. for 3 h to evaporate to dryness, and an 8M HCl solution was added to the obtained powder substance to make the volume 1 ml to obtain a column of treatment liquid;

[0058] The second column was filled with 100-200 mesh AG MP-1M resin, the inner diameter of the second column was 0.4 cm, and the height was 8 cm, that is, the filling size was 0.4 cm×8 cm, and a total of 1 ml of AG MP-1M resin was filled; after filling, 10 ml of MQ water and 5 ml of 8M HCl solution were used to elute the resin in sequence, and then 5 ml of MQ water was used to adjust the resin and remove bubbles to complete the preparation before elution, and then the first column treatment liquid was subjected to a second elution treatment according to the elution process shown in Table 2, and the final eluate was collected to obtain a copper recovery liquid.

[0059] Table 2 Elution process of the double column method used in Example 2

[0060]

[0061] This embodiment uses 37ml of eluent in total. It is found through the detection of the element composition of the geological sample copper recovery liquid that Na / Cu<0.05, Mg / Cu<0.03, Al / Cu<0.1, Ti / Cu<0.03, Fe, Ca, Ni, Cr, and Ba contents in the copper recovery liquid are all lower than 1ppb, and the presence of the above elements does not affect the subsequent determination, and the whole process does not introduce any elements that may interfere. The copper recovery rate of the first elution treatment is 99.23%, the copper recovery rate of the second elution treatment is 99.83%, and the full process recovery rate is 99.23%×99.83%=99.06%, which is close to 100%.

[0062] Example 3

[0063] According to the process of Example 1, copper recovery solutions of basalt standard samples BCR-2 (USGS), BIR-1a (USGS), soil standard sample NISTSRM 2711a, granodiorite standard sample GSP-2 (USGS), and argillaceous limestone standard sample GBW07108 (GSR-6) were obtained.

[0064] Based on the obtained copper recovery liquid, the copper isotope in each standard sample was detected by MC-ICP-MS mass spectrometry analysis.

[0065] The detection was carried out in low-resolution mode, and the method used for instrument mass discrimination correction was the Zn internal standard method. The corresponding MC-ICP-MS working parameter settings are shown in Table 3:

[0066] Table 3 MC-ICP-MS operating parameters (zinc internal standard method)

[0067] Working Parameters Numeric Working Parameters Numeric Operating voltage 2000V Integration time 4.097s RF Power 1250W Test block (cycle) 3(30) Skimmer Cone Ni(X) Faraday receiving cup L3 <![CDATA[ 63 With]]> Resolution Low (LR) Faraday receiving cup L1 <![CDATA[ 65 With]]> Injection rate 100μl / min Faraday receiving cup L2 <![CDATA[ 64 Zn]]> Nebulizer gas flow rate 1.0l / min Faraday receiving cup C <![CDATA[ 66 Zn]]> Sample carrier gas Ar Faraday receiver cup H1 <![CDATA[ 67 Zn]]> Cooling gas flow rate 16l / min Faraday receiving cup H2 <![CDATA[ 68 Zn]]> Auxiliary gas flow rate 1.0l / min Faraday Receiver Cup H4 <![CDATA[ 70 Zn]]>

[0068] The testing process includes:

[0069] The copper collection liquid is evaporated to dryness, dissolved in 3wt% HNO3, then evaporated to dryness again, and dissolved in 3wt% HNO3 to remove all chlorine to obtain a sample to be tested, and the sample to be tested is mixed with GSB Zn to contain 100ppb Cu and 200ppb Zn, and the resulting solution is used as a test sample; at the same time, a mixed solution of 100ppb copper isotope standard solution GSB Cu and 200ppb zinc isotope standard solution GSB Zn is used as an external standard solution for instrument parameter optimization; and NIST3114Cu and GSB Zn are mixed to contain 100ppb Cu and 200ppb Zn, and the resulting solution is used as a quality control sample for the measurement process, and finally a test sample containing an internal standard, an external standard solution, and a quality control sample are obtained. The above samples all contain 100ppb copper and 200ppb zinc, and the solvents used for dilution are all taken from the same barrel of 3wt% HNO3;

[0070] Before testing the test samples containing internal standards, external standard solutions and quality control samples, the sample injection system is cleaned with 3wt% HNO3. This process can prevent cross contamination between the test samples and external standard solutions, and is also used to monitor the blank of 3wt% HNO3 to deduct the value corresponding to the blank.

[0071] In order to correct the mass discrimination effect of the instrument, the copper external standard solution needs to be measured before and after the copper isotope composition of the test sample is determined. The measurement order is: 3wt% HNO3-external standard solution-quality control sample-external standard solution-test sample-external standard solution-test sample-external standard solution-test sample-external standard solution... Determine the ratio of quality control sample to test sample based on the stability of the instrument, insert a quality control sample every 5 to 10 samples tested, and no more than 20 samples are tested in each round;

[0072] After the test, the injection system was cleaned again with 3wt% HNO3;

[0073] To ensure the reliability of the data, each sample was tested at least three times each time, that is, the same sample was measured at least three times and its copper isotope ratio was obtained.

[0074] The mass discrimination correction of copper isotope ratio data can be performed using the SSB method, that is, the average fractionation coefficient of the external standard solution is calculated by performing isotope determination on the external standard solution with known isotope ratios before and after the sample to be tested. The obtained average fractionation coefficient is approximately considered to be the fractionation coefficient of the sample, and then the true isotope ratio of the sample is calculated:

[0075]

[0076] Where R is the corrected / true isotope ratio; r is the isotope ratio measured in the sample or standard; Ave.(r std ) is the average of the measured isotope ratios of the standards surrounding the sample.

[0077] In addition, the Cu isotope composition of the sample can be corrected using the regression equation obtained by the linear regression internal standard method. The specific process is as follows:

[0078]

[0079]

[0080] The relationship between the true value R and the measured value r is related to the fractionation coefficient f, and m represents the relative atomic mass of the nuclide. From this, we can get formulas (2) and (3); taking the logarithm of these two formulas, we get formulas (4) and (5).

[0081]

[0082]

[0083] Since the internal standard isotope and the Cu isotope can be linked through the fractionation coefficient, both sides of formula (5) are divided by the right side, and the right side is 1. Then the left side is substituted into the right side of formula (4) and the formula is formed into formula (6):

[0084]

[0085] Then, the interpolated external standard solution data of the sample is subjected to the above linear regression calculation to obtain an equation similar to formula (6), and the Zn (internal standard element) isotope ratio (r Zn ) into the equation, we get r Cu The result is taken as the Cu isotope ratio of the external standard solution. The Cu isotope ratio of the measured sample is divided by this result, subtracted by 1, and then multiplied by 1000 to obtain the δ 65 Cu(‰). The result is then converted to NIST SRM 976 (i.e. δ 65 Cu NISTSRM976 =δ 65 Cu GSBCu +0.44) to detect the δ 65 Cu NISTSRM976 The value is taken as the final copper isotope detection result.

[0086] The total program blank of this example is ~2ng, and the test results obtained are shown in Table 4 below:

[0087] Table 4 Copper isotope data of geological standard samples measured in Example 3

[0088]

[0089] It can be seen that the copper isotope ratio obtained in this example is consistent with the data measured by other existing technologies at home and abroad, indicating that this method can be used for copper isotope analysis and testing of geological samples.

[0090] The above embodiments are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A method for detecting copper isotopes in geological samples, characterized in that: The method comprises: obtaining a copper separation liquid by a separation and purification method of copper isotopes in a geological sample, and determining the copper isotope ratio in the copper separation liquid by a Zn internal standard method by MC-ICP-MS, wherein the separation and purification method of copper isotopes in a geological sample comprises: Digestion treatment is performed on geological samples containing copper to obtain a basic treatment solution; Performing a first pre-elution treatment on the first column, and performing a first elution treatment on the basic treatment liquid through the first column that has completed the first pre-elution treatment; The copper separation liquid obtained by the first elution treatment is heated and evaporated to dryness, and the volume is fixed with 8M HCl solution to obtain a first column treatment liquid; performing a second pre-elution treatment on the second column, and performing a second elution treatment on the first column treated liquid through the second column that has completed the second pre-elution treatment to obtain a copper recovery liquid; The first column is filled with 1 ml of 200-400 mesh AG1-X8 resin or 2 ml of 100-200 mesh AG MP-1M resin, and the second column is filled with 1 ml of 100-200 mesh AG MP-1M resin; the eluents used in the first elution treatment and the second elution treatment are both hydrochloric acid; The first elution pre-treatment comprises: eluting the first column with the following eluents in sequence: 10 ml of high-purity water, 5 ml of 6M hydrochloric acid, and 5 ml of high-purity water; The second pre-elution treatment includes: eluting the second column with the following eluents in sequence: 10 ml of high-purity water, 5 ml of 8M hydrochloric acid, and 5 ml of high-purity water; When the first column is filled with 1 ml of AG1-X8 resin with a mesh size of 200-400, the first elution treatment comprises sequentially eluting with the following eluents: 2 ml of 6M hydrochloric acid, 1 ml of 6M hydrochloric acid, 4 ml of 6M hydrochloric acid and 4 ml of 0.4M hydrochloric acid, and collecting the effluent obtained when 4 ml of 0.4M hydrochloric acid is used as the eluent, i.e., the copper separation solution; When the first column is filled with 2 ml of AG MP-1M resin with a mesh size of 100-200, the first elution treatment comprises sequentially eluting with the following eluents: 4 ml of 8M hydrochloric acid, 1 ml of 8M hydrochloric acid, 9 ml of 8M hydrochloric acid and 6 ml of 0.4M hydrochloric acid, and collecting the effluent obtained when 6 ml of 0.4M hydrochloric acid is used as the eluent, i.e., the copper separation solution; The second elution treatment includes sequentially washing with the following eluents: 2 ml of 8M hydrochloric acid, 1 ml of 8M hydrochloric acid, 4 ml of 8M hydrochloric acid and 10 ml of 8M hydrochloric acid, and collecting the effluent obtained when 10 ml of 8M hydrochloric acid is used as the eluent, i.e., the copper recovery liquid; The ratio of Zn isotopes used in the Zn internal standard method is m 66 / m 64 , where m represents the relative atomic mass of the nuclide.

2. The separation and purification method according to claim 1, characterized in that The digestion process comprises: (1) Weigh less than 30 mg of geological sample powder; (2) Add 1 ml of 15.8 M HNO3 and 0.5 ml of 23.1 M HF to the geological sample powder, seal it and heat it at 150-160 °C for 25-35 min, then perform ultrasonic treatment, and then alternately heat and ultrasonic treatment until the geological sample is completely dissolved or a small amount of insoluble white flocculent precipitate remains; (3) evaporating the solution obtained in step (2) at 150-160° C. to dryness, and cooling to room temperature; (4) Add 0.5 ml of 15.8 M HNO3 and 1.5 ml of 10.1 M HCl to the evaporated product obtained in step (3), seal the container and heat at 70-90°C until a clear solution is obtained; (5) After the clarified solution obtained in step (4) has cooled to room temperature, it is evaporated to dryness at 70-90°C in an open state; (6) Add 1 ml of 10.1 M HCl to the evaporated product obtained in step (5), seal the container and heat at 120-140° C. until a clear solution is obtained; (7) evaporating the clear solution obtained in step (6) at 120-140° C. to dryness, and cooling to room temperature; (8) Add 1 ml of 6M HCl to the evaporated product obtained in step (7) to obtain the basic treatment solution.

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