A standard substance of zinc blende and a preparation method thereof

Abstract

The application belongs to the technical field of standard substance preparation, and particularly relates to a sphalerite standard substance and a preparation method thereof. The preparation method of the sphalerite standard substance provided by the application comprises the following steps: mixing zinc acetate, ammonium sulfide, a multi-element mixed standard solution and water to perform a hydrothermal reaction, so as to obtain mixed sulfides mainly containing zinc sulfide; and performing hot-press sintering on the mixed sulfides mainly containing zinc sulfide, so as to obtain the sphalerite standard substance. The application combines the hydrothermal method and the hot-press method for the first time, and synthesizes a dense, solid and chemically uniform ZnS material, the matrix of which is consistent with the sphalerite crystal structure, the major components of which are consistent, and the element distribution of which is uniform, and the sulfur isotope composition of which is consistent with that of the sphalerite, so that the sphalerite standard substance is suitable for being used as a standard substance for sphalerite sulfur isotope analysis and trace element quantitative analysis.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of standard substance preparation, and particularly relates to a sphalerite standard substance and a preparation method thereof. BACKGROUND

[0002] Sulfide refers to a natural compound formed by combination of a metal element or a non-metal element with sulfur. Sulfide is the main source of many important metals, can often form large deposits with high reserves and easy mining, and has important economic significance. Sphalerite is one of the main ore minerals in magmatic hydrothermal deposits and MVT type deposits, and is also an important carrier of Ge, Ga, Cd, In and other dispersed metals.

[0003] Sulfur isotope is an important indicator for tracing the source of ore-forming material, the transport of ore-forming fluid, the mechanism of mineralization and the genesis of sulfide deposits. Microscale sulfur isotope information is more helpful for reconstructing the mineral formation process, revealing the characteristics of mineral growth and recrystallization, and deeply discussing the source of ore-forming material and the mechanism of mineralization.

[0004] Trace element geochemistry research is an important content of modern ore deposit research, and plays an important role in guiding the genesis of deposits, metallogenic regularity and metallogenic prediction. Microscale trace element analysis can directly help to distinguish ore-forming stages and indicate the source of ore-forming material according to the change of ore-forming elements.

[0005] At present, the sphalerite standard substance for sulfur isotope analysis and testing mainly includes NBS123 (American NIST standard, model number is SRM 8556), PSPT-3, SPH-1, PAS-GBW07270. Among them, NBS123 and SPH-1 are natural sphalerite, PSPT-3 is a powder pressed sheet, and PAS-GBW07270 is sintered by using a discharge plasma on the national standard GBW07270 powder. These materials do not elaborate the characteristics of trace elements in detail, and are not suitable for being used as standard substances for analyzing trace elements in sphalerite.

[0006] At present, the standard substances for trace elements include MASS-1 (American Geological Survey standard substance, full name is USGS MASS-1), MUL-ZnS-1, STDGL2b2 and STDGL3. Among them, MASS-1 is an international standard substance, which is a powder pressed sheet mixed by several sulfides. MUL-ZnS-1 has a matrix of a mixture of zinc sulfide, iron sulfide, cadmium sulfide and silver selenide, and is sintered into a solid after adding a trace element standard solution. The matrices of STDGL2b2 and STDGL3 are borate fusion cake, which are greatly different from the matrix of sulfide, and a correction factor needs to be introduced when correcting data. Table 1 shows the sulfur isotope composition and matrix composition of the above standard substances:

[0007] Table 1 Sulfur isotope composition and matrix components of the above-mentioned standard materials

[0008]

[0009]

[0010] Among the above sphalerite standard materials, there is no data on whether the trace elements are uniform for the standard materials tested for sulfur isotope analysis. And in the standard materials for trace element analysis, there is no complete consistency with the sphalerite matrix.

[0011] Nano-FeS2 is synthesized by using sulfur, ferrous chloride tetrahydrate and ethylene glycol as reaction reagents to synthesize pyrite nanoparticles by hydrothermal method, and then pressed into a cake-shaped solid standard material (Y. Feng, W. Zhang, Z. Hu, Y. Liu, K. Chen, J. Fu, J. Xie and Q. Shi, Journal of Analytical Atomic Spectrometry, 2018, 33, 2172-2183.); but the obtained solid is still a powder-shaped pressed cake, and the physical and chemical properties are quite different from those of natural sphalerite. SUMMARY

[0012] Therefore, the purpose of the present application is to provide a sphalerite standard material and a preparation method thereof. The sphalerite standard material prepared by the present application has a matrix consistent with natural sphalerite and is suitable for the analysis and determination of sulfur isotopes and trace elements.

[0013] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0014] The present application provides a preparation method of a sphalerite standard material, comprising the following steps:

[0015] Zinc acetate, ammonium sulfide, a multi-element mixed standard solution and water are mixed under alkaline conditions to perform a hydrothermal reaction to obtain a mixed sulfide mainly composed of zinc sulfide; the multi-element mixed standard solution comprises one or more of the following ions: As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ge, In, Mg, Mn, Na, Ni, Pb, Sc, Se, Te, V, Zn, Zr, Ga, Ag ions; the amount-of-substance ratio of the zinc acetate and the ammonium sulfide is 1:1;

[0016] The mixed sulfide mainly composed of zinc sulfide is subjected to hot-pressing sintering to obtain the sphalerite standard material.

[0017] Preferably, the ammonium sulfide is used in the form of an ammonium sulfide solution, the concentration of the ammonium sulfide solution is 20wt%, and the amount-of-substance ratio of the zinc acetate and the ammonium sulfide solution is 21.95g:30mL.

[0018] Preferably, the concentration of each element in the multi-element mixed standard solution is 100 mg / L, and the ratio of the amount of zinc acetate to the amount of the multi-element mixed standard solution is 21.95 g:2 mL.

[0019] Preferably, the pH value of the alkaline condition is 12.

[0020] Preferably, the temperature of the hydrothermal reaction is 240℃, and the time is 24 hours.

[0021] Preferably, the hydrothermal reaction further comprises solid-liquid separation, and the obtained solid is sequentially washed, dried and ground.

[0022] Preferably, the temperature of the drying is 150℃, and the time is 2 hours.

[0023] Preferably, the temperature of the hot-pressing sintering is 350℃, the pressure is 0.6 GPa, and the time of heat preservation and pressure preservation is 3.5-4.5 hours.

[0024] Preferably, the hot-pressing sintering further comprises: pressing a mixed sulfide cake mainly containing zinc sulfide, the pressure of the cake is 1.5 t, and the time is 1-5 minutes.

[0025] The application further provides a sphalerite standard substance prepared by the preparation method, which comprises Zn, S and trace elements, the sulfur isotope ratio of the sphalerite standard substance is +16.5-17.5‰ (2s), the content of Zn in the sphalerite standard substance is 66.6-67.9 wt%, and the content of S is 32.0-32.8 wt%.

[0026] Compared with the prior art, the application has the following beneficial effects:

[0027] The application provides a preparation method of a sphalerite standard substance, comprising the following steps: mixing zinc acetate, ammonium sulfide, a multi-element mixed standard solution and water to perform a hydrothermal reaction, so as to obtain a mixed sulfide mainly composed of zinc sulfide; the multi-element mixed standard solution comprises one or more of the following ions: As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ge, In, Mg, Mn, Na, Ni, Pb, Sc, Se, Te, V, Zn, Zr, Ga, Ag ions; and the mixed sulfide mainly composed of zinc sulfide is subjected to hot-press sintering, so as to obtain the sphalerite standard substance. The hydrothermal method and the hot-press method are combined for the first time, and the ZnS material with the characteristics of compactness, firmness and uniform chemical properties is synthesized, the matrix is consistent with the sphalerite crystal structure (regular cubic system, face-centered cubic lattice), the major components are consistent, and the sphalerite sulfur isotope composition is consistent and the element distribution is uniform, so that the sphalerite sulfur isotope analysis and the trace element quantitative analysis can be performed.

[0028] The data of the embodiments show that the sphalerite standard substance prepared by the application is consistent with the natural sphalerite in physical and chemical properties, and can be used as the standard substance for the LA-MC-ICP-MS determination of the sphalerite sulfur isotope and the LA-ICP-MS determination of the trace elements of the sphalerite. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the application or the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings described below are only some embodiments of the application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0030] Figure 1 It is a preparation flow chart of the sphalerite standard substance of example 1.

[0031] Figures 2 to 4 It is a laser ablation characteristic map of the ZnS material synthesized in example 1.

[0032] Figures 5 to 7 It is a laser ablation characteristic map of NBS123.

[0033] Figures 8 to 10 It is a laser ablation characteristic map of MASS-1.

[0034] Figures 11 to 13 It is a laser ablation characteristic map of the powder tablet of the nanoparticle.

[0035] Figure 14 It is an XRD map of the ZnS powder synthesized by the sphalerite nanoparticle, the sintered ZnS block and other reagents (zinc acetate and thiourea).

[0036] Figure 15 TEM and HRTEM images of ZnS material synthesized for Example 1;

[0037] Figure 16 Correction of results of NBS123 and PAS-GBW07270 sulfur isotope ratio with ZnS material synthesized for Example 1;

[0038] Figure 17 Results of multi-laboratory comparison and multi-method comparison for each element. DETAILED DESCRIPTION

[0039] The present application provides a preparation method of a sphalerite standard material, comprising the following steps:

[0040] Zinc acetate, ammonium sulfide, a multi-element mixed standard solution and water are mixed under alkaline conditions to perform a hydrothermal reaction to obtain a mixed sulfide mainly containing zinc sulfide; the multi-element mixed standard solution comprises one or more of the following ions: As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ge, In, Mg, Mn, Na, Ni, Pb, Sc, Se, Te, V, Zn, Zr, Ga, Ag ions; the molar ratio of zinc acetate to ammonium sulfide is 1:1.

[0041] The mixed sulfide mainly containing zinc sulfide is subjected to hot-press sintering to obtain the sphalerite standard material.

[0042] In the present application, the materials and equipment used are commercially available in the art unless otherwise specified.

[0043] In the present application, zinc acetate, ammonium sulfide, a multi-element mixed standard solution and water are mixed under alkaline conditions to perform a hydrothermal reaction to obtain a mixed sulfide mainly containing zinc sulfide; the multi-element mixed standard solution comprises one or more of the following ions: As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ge, In, Mg, Mn, Na, Ni, Pb, Sc, Se, Te, V, Zn, Zr, Ga, Ag ions; the molar ratio of zinc acetate to ammonium sulfide is 1:1.

[0044] In the present application, the zinc acetate is a zinc source, and the ammonium sulfide is a sulfur source; the ammonium sulfide is preferably used in the form of an ammonium sulfide solution, the concentration of the ammonium sulfide solution is preferably 20wt%, and the amount ratio of zinc acetate to ammonium sulfide solution is preferably 21.95g:30mL.

[0045] In the present application, zinc acetate and water are first mixed, then the multi-element mixed standard solution is added for second mixing, and finally ammonium sulfide is added for third mixing.

[0046] In the present application, the ratio of the amount of zinc acetate and water is preferably 21.95 g:100 mL, and the concentration of the zinc acetate aqueous solution obtained by the first mixing of zinc acetate and water is preferably 1 mmol / L.

[0047] In the present application, the concentration of each element in the multi-element mixed standard solution is preferably 100 mg / L, and the ratio of the amount of zinc acetate and the multi-element mixed standard solution is preferably 21.95 g:2 mL.

[0048] In the present application, after the mixing of zinc acetate, ammonium sulfide, the multi-element mixed standard solution and water, the pH value is preferably adjusted, and the pH value of the mixed solution after the adjustment is preferably 12. The pH adjuster used for the adjustment is preferably NaOH.

[0049] In the present application, the temperature of the hydrothermal reaction is preferably 240℃, and the time is preferably 24 hours. The hydrothermal reaction is preferably carried out in a high-pressure kettle with a Teflon lining. The hydrothermal process is carried out in an anaerobic, high-temperature environment, which is the best growth environment for sphalerite.

[0050] In the present application, after the hydrothermal reaction, the solid-liquid separation is preferably carried out, and the obtained solid is sequentially washed, dried and ground. The solid-liquid separation is preferably carried out by centrifugation. The washing preferably includes sequential water washing and ethanol washing. The drying temperature is preferably 150℃, and the time is preferably 2 hours. The drying temperature and time of the present application can sufficiently dry the product. The grinding time is preferably 5 minutes.

[0051] After obtaining the mixed sulfide mainly containing zinc sulfide, the mixed sulfide mainly containing zinc sulfide is subjected to hot-pressing sintering to obtain the sphalerite standard material.

[0052] In the present application, before the hot-pressing sintering, the mixed sulfide mainly containing zinc sulfide is preferably pressed into a cake (pressed into a round cake). The pressing into a cake is preferably carried out in a hydraulic press. The pressure of the hydraulic press is preferably 1.5 t, and the time for maintaining the pressure is preferably 1-5 minutes. The size of the obtained round cake is preferably 8 mm, 9.2 mm (diameter, height).

[0053] In the present application, the temperature of the hot-pressing sintering is preferably 350℃, the pressure is preferably 0.6 GPa, and the time for maintaining the temperature and pressure is preferably 3.5-4.5 hours, more preferably 4 hours. The time for maintaining the temperature and pressure of the present application does not cause phase transition.

[0054] If only the mixed sulfide powder mainly containing zinc sulfide is pressed into a cake, the powder cake has loose texture and cannot be polished, and is easy to absorb moisture. The hot-pressing sintering of the present application can sinter the powder into a ceramic-like solid to obtain a block-shaped body.

[0055] The sphalerite standard substance prepared by the preparation method has Zn, S and trace elements, and the sulfur isotope ratio of the sphalerite standard substance is +16.5-17.5 ‰ (2s), the content of Zn in the sphalerite standard substance is 66.6-67.9 wt%, and the content of S is 32.0-32.8 wt%.

[0056] In the present application, the sulfur isotope ratio of the sphalerite standard substance is preferably +17.22 ± 0.20 ‰ (2s), the content of Zn in the sphalerite standard substance is preferably 66.71 wt%, and the content of S is 32.72 wt%.

[0057] In the present application, the trace elements include one or more of As, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ge, In, Mg, Mn, Na, Ni, Pb, Sc, Se, Te, V, Zr, Ga and Ag. The Zn ions in the multi-element mixed standard solution form zinc sulfide as the main component of the sphalerite standard substance; after being prepared into the sphalerite standard substance, the Ca content test result has a large deviation, and cannot be used as a trace element correction standard substance, and the trace elements in the present application can be used as the trace element correction standard substance.

[0058] In the present application, the content of a single trace element in the sphalerite standard substance is preferably several ppm to several tens of ppm.

[0059] In the present application, the sphalerite standard substance is a regular cubic crystal system, and the space group is F-43m It corresponds to (111), (200), (220), (311), (222), (400) crystal faces at 28.53°, 33.061°, 47.454°, 56.307°, 59.051° and 69.368 (2θ°), respectively.

[0060] The sphalerite standard substance provided by the present application is suitable for LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometer) and LA-MC-ICP-MS (laser ablation multi-receiving inductively coupled plasma mass spectrometer) micro-area in-situ analysis, and makes up for the shortage that there is still a lack of matching with the sphalerite matrix and simultaneously serving as an isotopic and trace element correction standard substance.

[0061] In order to further illustrate the present application, the sphalerite standard substance and the preparation method thereof provided by the present application are described in detail below in combination with the drawings and examples, but they cannot be understood as limiting the protection scope of the present application.

[0062] Example 1

[0063] 1, Hydrothermal reaction process:

[0064] 1) Select zinc acetate as zinc source, ammonium sulfide as sulfur source.

[0065] 2) Dissolve 21.95 g (0.1 mol) of zinc acetate in 100 mL of deionized water (solvent).

[0066] 3) Add 2 mL of multi-element standard solution (As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, In, Mg, Mn, Na, Ni, Pb, Sc, Se, Te, V, Zn, Zr, each at a concentration of 100 ppm), 2 mL of Ga single standard solution (at a concentration of 100 ppm), and 2 mL of Ag single standard solution (at a concentration of 100 ppm).

[0067] 4) While stirring with a magnetic stirrer, add 30 mL of ammonium sulfide solution (at a concentration of 20 wt%, containing 0.1 mol of ammonium sulfide).

[0068] 5) Adjust the pH value to 12 with NaOH.

[0069] 6) Heat to 240℃ in a Teflon-lined autoclave for 24 hours.

[0070] 7) Naturally cool to room temperature, centrifuge, and then repeatedly wash with deionized water and ethanol.

[0071] 8) Transfer to a vacuum oven and bake at 150℃ for 2 hours.

[0072] 9) Grind the solid in an agate mortar for 5 minutes to obtain ZnS-based nanoparticles.

[0073] 2. Hot-pressing sintering process:

[0074] 1) Place 0.75 g of powder in a hydraulic press and press at a pressure of 1.5 t for 1 minute to form a round cake (8 mm in diameter, 9.2 mm high).

[0075] 2) Place the round cake in a platinum tube and seal.

[0076] 3) Place the platinum tube in a vertical press and heat at 350℃ and 0.6 GPa for 4 hours for high-pressure sintering to obtain a ZnS-based solid material (standard material of sphalerite).

[0077] Figure 1 The preparation flowchart of the sphalerite standard material of Example 1 of the present application is divided into a hydrothermal synthesis process and a hot-pressing sintering process.

[0078] Comparative Example 1

[0079] The difference from Example 1 is that the sulfur source is replaced by thioacetamide (0.1 mol) and the solvent is replaced by anhydrous ethanol, and the rest of the conditions are the same as in Example 1.

[0080] Comparative Example 2

[0081] The difference from Example 1 is that the sulfur source is replaced by thiourea (0.1 mol), and the rest of the conditions are the same as in Example 1.

[0082] The theoretical density of natural sphalerite is 4.111 g / cm 3 The measured density of the material synthesized in Example 1 of the present application is 4.106 g / cm 3 , which is consistent with that of natural sphalerite.

[0083] The sulfur isotope ratio is δ 34 S, which is 34 S and 32 S, can be used to trace the source of the material. The consistency of the sulfur isotope composition indicates that there is no isotopic fractionation in the synthesis process. The sulfur isotope ratio δ 34 S of the material synthesized in Example 1 of the present application is +17.22 ± 0.20 ‰ (2s), the sulfur isotope ratio of the standard material synthesized in Comparative Example 1 is 46.26 ‰, and the sulfur isotope ratio of the standard material synthesized in Comparative Example 2 is 36.04 ‰. The isotope ratio is too heavy (the sulfur isotope ratio needs to be as close to 0 as possible), which is not suitable for correcting the sulfur isotope ratio of natural minerals.

[0084] Table 2 is the determination results of the sphalerite standard material prepared in Example 1. The content of Zn in the sphalerite standard material is 66.68-66.73 wt%, and the content of S is 32.70-32.73 wt% (the range value of 240 points tested by LA-ICP-MS). The occurrence states of different trace elements are different, some of which enter the ZnS lattice, and some of which adhere to the crystal in the form of colloids. The content of trace elements in the sphalerite standard material is in the range of several ppm to several tens of ppm.

[0085] Table 2 is the determination results of the sphalerite standard material prepared in Example 1.

[0086]

[0087]

[0088] The block sintered in Example 1 of the present application can be polished and is not afraid of oxidation, and can be reused. The laser ablation characteristic map is as shown in Figures 2 to 13 , wherein Figures 2 to 4 is the material synthesized in Example 1 of the present application, Figures 5 to 7 is NBS123, Figures 8 to 10 is MASS-1, Figures 11 to 13The powder of the nanoparticles was pressed into a tablet (the material of Example 1 was directly pressed into a tablet after hydrothermal synthesis). It can be seen that the morphology of the etch pits of the ZnS material of Example 1 is perfect, and the etched aerosol is mostly small particles, which is close to the etch pits of natural sphalerite NBS123. The LA-ICP-MS was used to etch the synthesized material, and the collected element spectrum is smooth without small abnormal peaks. MASS-1 is a powder tablet, and the aerosol particles around the etch pits are large and loose in texture, and the spectrum collected by LA-ICP-MS has many small peaks.

[0089] Figure 14 Figures a and b are XRD patterns of the synthesized sphalerite nanoparticles and the ZnS bulk after sintering, respectively, which show that no wurtzite conversion occurs in the synthesis process; figure c shows that the wurtzite conversion is easy to occur when other reagents (ZnS powder synthesized by zinc acetate and thiourea, Comparative Example 2) are used for synthesis, and the wurtzite conversion will occur no matter how the synthesis temperature is set.

[0090] The bulk material of Example 1 was ground into powder for TEM and HRTEM tests, Figure 15 Figures are TEM and HRTEM data of the ZnS material of Example 1, which show that the synthesized material is sphalerite single crystal, the particle size is 100-800 nm, and the crystal structure is regular cubic single crystal.

[0091] The same synthesis method as that of Example 1 was used to synthesize once a month (a total of 5 times), and then the isotopic ratio was measured. The final sulfur isotopic ratio of each solid material is consistent, which is +16.86±0.36‰ (2s, n=19), +16.90±0.32‰ (2s, n=50), +16.93±0.21‰ (2s, n=30), +16.93±0.30‰ (2s, n=21), +16.97±0.26‰ (2s, n=20), which shows that the synthesis method can ensure the stability and uniformity of the sulfur isotopic ratio. Then, the ZnS material of Example 1 was used to correct NBS123 and PAS-GBW07270, and the results are shown in Figure 16 Figures, and the obtained sulfur isotopic ratio is consistent with the recommended value, which shows that the synthesized material of Example 1 is completely feasible as a sulfur isotopic correction material.

[0092] The ZnS solid synthesized in Example 1 was cut into 8 parts of the same size, and 70 points of each part were measured by LA-MC-ICP-MS, all of which were calibrated by NBS123, and the obtained sulfur isotope ratios were consistent, being +17.07±0.20‰(2s, n=70), +17.10±0.16‰(2s, n=70), +17.13±0.18‰(2s, n=70), +17.18±0.20‰(2s, n=70), +17.09±0.20‰(2s, n=70), +17.13±0.24‰(2s, n=70), +17.09±0.20‰(2s, n=70) and +17.11±0.20‰(2s, n=70) respectively, proving the uniformity of the synthesized material.

[0093] First, the ZnS synthesized in Example 1 was detected by ICP-MS to obtain the content of each element. Then, the same piece of ZnS material was detected by LA-ICP-MS in three laboratories respectively, and 20 points were measured in each laboratory. The content of each element obtained in each laboratory was compared with the ICP-MS test result to calculate the relative deviation (Relative deviation) as the Y axis, and the X axis was each element to obtain the corresponding scatter plot as shown in Figure 17 The conclusion obtained in each laboratory was consistent and consistent with the ICP-MS test result. It is proved that the results of multi-laboratory comparison and multi-method comparison are consistent, and the element distribution is uniform.

[0094] The sphalerite standard material prepared by the present application has consistent physical and chemical properties with natural sphalerite, and can be used as a standard material for LA-MC-ICP-MS determination of sphalerite sulfur isotope and can be used in LA-ICP-MS determination of sphalerite trace elements. The sphalerite standard material has uniform element distribution and consistent sulfur isotope composition, and has consistent matrix and sphalerite crystal structure and consistent major components (Zn and S).

[0095] Although the above examples have made a detailed description of the present application, it is only a part of the embodiments of the present application, but not all the embodiments, and other embodiments can be obtained according to the embodiments of the present application without creative labor, which belong to the protection scope of the present application.

Claims

1. A method for preparing a sphalerite standard material, characterized by, The method comprises the following steps: Zinc acetate, ammonium sulfide, a multi-element mixed standard solution and water are mixed under alkaline conditions to perform a hydrothermal reaction to obtain a mixed sulfide mainly containing zinc sulfide; the multi-element mixed standard solution contains one or more of the following ions: As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ge, In, Mg, Mn, Na, Ni, Pb, Sc, Se, Te, V, Zn, Zr, Ga, Ag ions; the molar ratio of zinc acetate to ammonium sulfide is 1:1; The mixed sulfide mainly containing zinc sulfide is subjected to hot-pressing sintering to obtain the sphalerite standard substance.

2. The production method according to claim 1, characterized by, The ammonium sulfide is used in the form of an ammonium sulfide solution, the concentration of the ammonium sulfide solution is 20 wt%, and the amount ratio of zinc acetate to the ammonium sulfide solution is 21.95 g:30 mL.

3. The production method according to claim 1 or 2, characterized by, The concentration of each element in the multi-element mixed standard solution is 100 mg / L, and the amount ratio of zinc acetate to the multi-element mixed standard solution is 21.95 g:2 mL.

4. The production method according to claim 1, characterized by, The pH value of the alkaline condition is 12.

5. The preparation method according to claim 1, characterized in that, The temperature of the hydrothermal reaction is 240 DEG C, and the time is 24 hours.

6. The production method according to claim 1 or 5, characterized by, The hydrothermal reaction further comprises solid-liquid separation, and the obtained solid is sequentially washed, dried and ground.

7. The production method according to claim 6, wherein The temperature of the drying is 150 DEG C, and the time is 2 hours.

8. The method of claim 1, wherein, The temperature of the hot-pressing sintering is 350 DEG C, the pressure is 0.6 GPa, and the time of heat preservation and pressure preservation is 3.5-4.5 hours.

9. The production method according to claim 8, characterized by, The hot-pressing sintering further comprises: pressing the mixed sulfide mainly containing zinc sulfide into a cake, the pressure of the cake is 1.5 t, and the time is 1-5 minutes.

10. The sphalerite reference material produced by the method of any one of claims 1 to 9, characterized in that, The sphalerite standard substance contains Zn, S and trace elements, the sulfur isotope ratio of the sphalerite standard substance is +16.5-17.5 ‰ (2s), the content of Zn in the sphalerite standard substance is 66.6-67.9 wt%, and the content of S is 32.0-32.8 wt%.

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