Method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules

Abstract

The present invention relates to the technical field of isotope determination, and discloses a method for determining the compositions of beryllium and aluminum isotopes in deep-sea ferromanganese nodules, comprising the following steps: subjecting the deep-sea ferromanganese nodules to acid extraction to obtain a test sample; 9 Be carrier, 27 Al carrier are added to the test sample, and then the mixture is transferred into an adsorption column filled with a composite exchange resin. After oscillating adsorption, hydrochloric acid is used for leaching, and the iron element leachate, beryllium element leachate, and aluminum element leachate are collected; the concentrations of the iron element leachate, beryllium element leachate, and aluminum element leachate are measured by an inductively coupled plasma mass spectrometer; ammonia water is added to the iron element leachate, beryllium element leachate, and aluminum element leachate respectively, and the precipitate is collected by centrifugation. The precipitate is sintered to obtain an oxide. The oxide is mixed and ground with silver powder, niobium powder, and copper powder respectively to obtain a target sample, and the target sample is placed in the target disk of an accelerator mass spectrometer for determination.

Description

Technical Field

[0001] The present invention relates to the technical field of isotope determination, and specifically provides a method for determining the compositions of beryllium and aluminum isotopes in deep-sea ferromanganese nodules. Background Art

[0002] Ocean polymetallic nodules, which are polymetallic deposits growing on the deep seabed, are also known as deep-sea manganese nodules or manganese ore balls, manganese ore nodules, and manganese nodules. They mainly consist of manganese and iron oxides and hydroxides, contain various metal elements such as copper, nickel, and cobalt, and mostly exist in nodular forms. Due to their huge reserves and continuous growth, they have become a huge potential metal resource; ferromanganese nodules not only contain rich rare metal resources, but their growth process also records information on paleoenvironmental changes.

[0003] In deep-sea ferromanganese nodules, beryllium exists as Be 2+ , aluminum exists as Al 3+ , and iron exists as Fe 2+ and Fe 3+ . By using different chemical processes to separately extract the three isotopes of beryllium, aluminum, and iron, it is impossible to simultaneously extract them from a single nodule sample. Moreover, using ion exchange resins will adsorb other impurity metals, and the directional adsorption is poor, resulting in the adsorption of impurity metals into the adsorption column filled with composite exchange resins, and the collected metal isotopes are impure, affecting the detection effect. Summary of the Invention

[0004] The present invention provides a method for determining the compositions of beryllium and aluminum isotopes in deep-sea ferromanganese nodules, which solves the problem that the prior art needs to separately extract the three isotopes of beryllium, aluminum, and iron and cannot simultaneously extract them from a single nodule sample.

[0005] Technical Solution of the Invention:

[0006] A method for determining the compositions of beryllium and aluminum isotopes in deep-sea ferromanganese nodules includes the following steps:

[0007] S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample;

[0008] S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite exchange resin, oscillate and adsorb for 20 - 30 min, then perform leaching with hydrochloric acid, and collect the iron element leachate, beryllium element leachate, and aluminum element leachate;

[0009] S3. Use an inductively coupled plasma atomic emission spectrometer / mass spectrometer ICP - AES / MS to measure the concentrations of iron element, beryllium element, and aluminum element in the solution taken out in S1, and the concentrations of part of the iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2;

[0010] S4. Add ammonia water to the iron element leachate, beryllium element leachate, and aluminum element leachate respectively to adjust the pH value to 8 - 9, centrifuge to collect the precipitate, sinter the precipitate at 850 - 950 °C for 1 - 2 h to obtain the oxide, mix the oxide with silver powder, niobium powder, and copper powder respectively, grind them to obtain the target sample, and place the target sample in the target disk of the accelerator mass spectrometer for determination;

[0011] The composite ion exchange resin is obtained by mixing and reacting phosphorylated cation exchange resin, iron element adsorbent material, oxalic acid, and lignin;

[0012] The iron element adsorbent material is obtained by mixing and reacting activated carbon, ferric trichloride hexahydrate, and cetyltrimethylammonium bromide, and then mixing with amino silane and anion exchange resin;

[0013] The phosphorylated cation exchange resin is obtained by crushing, grinding, and sieving the cation exchange resin, and then mixing and reacting with 3-(trihydroxysilyl)propyl methyl phosphate;

[0014] Further, in step S1, the specific steps of acid extraction of deep - sea ferromanganese nodules are as follows:

[0015] Place the deep - sea ferromanganese nodule sample in a centrifuge tube, add deionized water, hydrochloric acid, and hydrogen peroxide, oscillate and react, soak overnight, and centrifuge to collect the supernatant a and residue a;

[0016] Add hydrochloric acid to residue a, stir well, soak overnight, and centrifuge to collect supernatant b and residue b;

[0017] Place residue b in deionized water, mix evenly, centrifuge to collect supernatant c, mix supernatant c, supernatant a, and supernatant b, evaporate to a curd - like state, then add hydrochloric acid to dissolve, collect the solution, repeat the dissolution 5 times and then centrifuge to collect the supernatant to obtain the test sample. Take a quantitative test sample and measure the original concentrations of iron element, beryllium element, and aluminum element using inductively coupled plasma optical / mass spectrometry ICP - AES / MS. Further, the specific operation of step S2 is as follows:

[0018] Put the test sample, 9 Be carrier, 27 Al carrier into the adsorption column filled with the composite ion exchange resin, oscillate and adsorb for 20 - 30 min, leach with hydrochloric acid with a concentration of 0.05 - 0.1 mol / L to 1 - 2.5 CV, collect the iron element leachate, leach with hydrochloric acid with a concentration of 0.5 - 1.0 mol / L to 4.5 - 6.5 CV, collect the beryllium element leachate, leach with hydrochloric acid with a concentration of 2 - 3 mol / L to 8.5 - 10.5 CV, and collect the aluminum element leachate.

[0019] Further, the test sample, 9 Be carrier,27 The mass ratio of the Al carrier is 4.6:0.5:0.5.

[0020] Further, in step S4, the specific operation is as follows:

[0021] Mix the iron element leaching solution with ammonia water, adjust the pH to 8 - 9, centrifuge to collect the precipitate, sinter the precipitate at 850 - 950 °C for 1 - 2 h to obtain iron oxide, mix the iron oxide and silver powder, grind them to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0022] Mix the beryllium element leaching solution with ammonia water, adjust the pH to 8 - 9, centrifuge to collect the precipitate, sinter the precipitate at 850 - 950 °C for 1 - 2 h to obtain beryllium oxide, mix the beryllium oxide and niobium powder, grind them to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0023] Mix the aluminum element leaching solution with ammonia water, adjust the pH to 8 - 9, centrifuge to collect the precipitate, sinter the precipitate at 850 - 950 °C for 1 - 2 h to obtain aluminum oxide, mix the aluminum oxide and copper powder, grind them to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement.

[0024] Further, the mass ratio of iron oxide and silver powder is 3:1.

[0025] Further, the mass ratio of beryllium oxide and niobium powder is 3:1.

[0026] Further, the mass ratio of aluminum oxide and copper powder is 5:1.

[0027] Further, the size of the adsorption column: the diameter is 50 - 60 mm and the height is 140 - 160 mm.

[0028] Further, 1 CV = 16 mL.

[0029] Further, the composite ion exchange resin is specifically prepared by the following steps:

[0030] A1. Add ferric chloride hexahydrate to deionized water, stir evenly, add cetyltrimethylammonium bromide, sodium hydroxide and activated carbon, stir and mix at a rate of 500 - 600 r / min for 30 - 40 min, stir and react at 110 - 130 °C for 10 - 12 h, cool to room temperature, filter, wash, and dry to obtain activated carbon loaded with nano - iron oxide;

[0031] A2. Add the anion exchange resin to deionized water and ethanol, stir evenly, add the activated carbon loaded with nano - iron oxide and aminosilane, stir and mix at 60 - 70 °C for 2 - 5 h, filter, wash, and dry to obtain the iron ion adsorption material;

[0032] A3. After the cation exchange resin is crushed, ground, and sieved, the sieve aperture is 110 - 150 mesh to obtain powdery resin particles. The powdery resin particles are added to deionized water and ethanol, stirred evenly, 3-(trihydroxysilyl)propyl methyl phosphate is added, and stirred and reacted for 1 - 2 h. After filtration, washing, and drying, phosphorylated cation exchange resin is obtained;

[0033] A4. Lignin and deionized water are mixed and stirred evenly. An aqueous sodium hydroxide solution is added to adjust the pH to 10 - 11. Oxalic acid, phosphorylated cation exchange resin, and iron ion adsorption material are added, and stirred and mixed at 50 - 60 °C for 10 - 20 min. It is cooled to room temperature, left standing overnight, filtered, washed, and dried to obtain composite exchange resin.

[0034] Further, during the above A1 reaction process, the activated carbon has excellent adsorption performance and can adsorb iron ions in ferric chloride hexahydrate into the pores of the activated carbon. And cetyltrimethylammonium bromide is used as a surfactant, and sodium hydroxide provides hydroxide ions to form hydroxides in the pores of the activated carbon. Through hydrothermal reaction, the hydroxides are thermally decomposed to form iron oxide crystals. As the reaction proceeds, the iron oxide crystals grow, realizing the synthesis of nano - iron oxide in the pores of the activated carbon to obtain activated carbon loaded with nano - iron oxide.

[0035] Further, during the above A2 reaction process, the silanol groups generated by the hydrolysis of amino silane can combine with the hydroxyl groups on the surface of the activated carbon loaded with nano - iron oxide. And the amino groups of amino silane carry positive charges and can electrostatically combine with the anionic groups in the anion exchange resin, making the anion exchange resin adhere to the surface of the activated carbon loaded with nano - iron oxide to obtain iron ion adsorption material.

[0036] Further, during the above A3 reaction process, after the cation exchange resin is crushed, ground, and sieved, the sieve aperture is 150 mesh to form a porous adsorption resin with a sieve aperture of 0.1 - 0.5 mm; the silanol groups generated by the hydrolysis of 3-(trihydroxysilyl)propyl methyl phosphate can chemically combine with the cationic groups in the cation exchange resin, making 3-(trihydroxysilyl)propyl methyl phosphate grafted on the cation exchange resin to complete the phosphorylated cation exchange resin.

[0037] Further, during the above A4 reaction process, oxalic acid is used as a cross - linker and can react with the phenolic hydroxyl groups on lignin to form a cross - linked porous structure. And the phosphorylated cation exchange resin and iron ion adsorption material can also be embedded in the porous structure, having excellent adsorption performance for metal ions, improving the extraction rate of iron, aluminum, and beryllium elements in the iron - manganese nodule test sample, and further improving the high - efficiency detection efficiency of metal elements in iron - manganese nodules.

[0038] Further, in step A1, the dosage ratio of ferric chloride hexahydrate, deionized water, cetyltrimethylammonium bromide, sodium hydroxide and activated carbon is (1.2 - 1.4) g : (35 - 45) mL : (0.4 - 0.6) g : (0.2 - 0.4) g : (2 - 3) g.

[0039] Further, in step A2, the mass ratio of the anion exchange resin, deionized water, ethanol, activated carbon loaded with nano iron oxide and aminosilane is (5.6 - 5.8) g : (20 - 30) mL : (75 - 85) mL : (10 - 11) g : (0.5 - 0.9) g.

[0040] Further, in step A3, the dosage ratio of the powdered resin particles, deionized water, ethanol and 3-(trihydroxysilyl)propylmethylphosphonate is (1.6 - 1.8) g : (8 - 12) mL : (25 - 35) mL : (0.2 - 0.4) g.

[0041] Further, in step A4, the dosage ratio of lignin, deionized water, oxalic acid, phosphorylated cation exchange resin and iron ion adsorbent is (8 - 12) g : (90 - 120) mL : (1.2 - 1.4) g : (3 - 4) g : (3 - 3.6) g.

[0042] Further, the carboxyl content of lignin is 1.6 - 1.66 mmol / g, Hunan Taigelin Paper Group Co., Ltd.

[0043] Further, the aminosilane is γ-aminopropyltriethoxysilane.

[0044] The present invention has the following beneficial effects:

[0045] (1) In the technical solution of the present invention, nano iron oxide is synthesized in the pores of activated carbon to obtain activated carbon loaded with nano iron oxide. The activated carbon has a large specific surface area and pore structure, providing more adsorption space for iron ions. Moreover, in an acidic environment, iron ions have higher activity than aluminum and beryllium elements. The hydroxyl groups carried on the surface of the synthesized nano iron oxide can adsorb iron ions directionally, reducing the interference of other metal ions and improving the extraction efficiency. In addition, it avoids the adsorption of impurity metals into the adsorption column filled with composite exchange resin, resulting in impure collected metal isotopes and affecting the detection effect. The anion exchange resin is adsorbed on the surface of the activated carbon loaded with nano iron oxide through aminosilane to obtain an iron ion adsorption material. On the one hand, in an acidic environment, iron elements in the iron-manganese nodule test sample can combine with chloride ions to form ferric chloride ions, which can exchange with the anion groups in the anion exchange resin, enabling the iron elements to be adsorbed into the iron ion adsorption material. On the other hand, the activated carbon loaded with nano iron oxide contained in the iron ion adsorption material provides additional adsorption sites and adsorption capacity, improving the directional extraction of iron isotopes in iron-manganese nodules, enhancing the extraction efficiency, reducing the detection error, and the rigid framework of the activated carbon inhibits the swelling and deformation of the anion resin in concentrated acid.

[0046] (2) In the technical solution of the present invention, the cation exchange resin is crushed, ground, and sieved, and the mesh aperture of the sieve is 150 meshes to form a porous adsorption resin. Moreover, the cation groups contained in the cation exchange resin will dissociate hydrogen ions in an acidic solution, making the resin surface negatively charged, so that it can adsorb and combine with aluminum and beryllium elements in the iron-manganese nodule test sample to complete the extraction of aluminum and beryllium elements. 3-(trihydroxysilyl)propyl methyl phosphate is grafted onto the cation exchange resin to complete the phosphorylation of the cation exchange resin, introducing phosphate groups onto the porous cation exchange resin. On the one hand, the phosphate groups can complex with aluminum elements in the iron-manganese nodule test sample to form specific adsorption and complete the adsorption performance of aluminum elements. On the other hand, the contained phosphate groups can form a stable complex with beryllium elements through beryllium-oxygen-phosphorus to complete the directional adsorption of beryllium elements.

[0047] (3) In the technical solution of the present invention, the phosphorylated cation exchange resin, the iron ion adsorbing material, oxalic acid, and lignin are mixed and reacted to form a cross-linked porous structure, and the phosphorylated cation exchange resin and the iron ion adsorbing material can also be embedded in the porous structure, increasing the cross-linking density, improving the porosity, having excellent adsorption performance for metal ions, improving the extraction rates of iron, aluminum, and beryllium elements in the ferromanganese nodule test sample, and further improving the detection accuracy of metal elements in the ferromanganese nodule; the phosphorylated cation exchange resin and the iron ion adsorbing material are compounded to form a composite exchange resin and filled into the adsorption column, which can simultaneously extract the three isotopes of iron, beryllium, and aluminum in the ferromanganese nodule, reducing the sample demand, reducing the deviation introduced by the analysis of multiple samples, greatly shortening the experimental time and the types of reagents, and improving the work efficiency and economic benefits.

[0048] (4) In the technical solution of the present invention, acid extraction of deep-sea ferromanganese nodules can remove insoluble impurities and interfering substances in the deep-sea ferromanganese nodules, improve the extraction effect of metal elements in the deep-sea ferromanganese nodules, reduce the interference with the analysis results, and improve the accuracy of the analysis. In addition, through multiple steps of hydrochloric acid solution and centrifugation, the metal element components in the deep-sea ferromanganese nodules can be further enriched, improving the extraction purity and detectability. Specific embodiments

[0049] The following will describe clearly and completely the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0050] The raw materials used in the embodiments of the present invention are as follows, and all the reagents used are of analytical grade.

[0051] Among them, the activated carbon has a particle size of 3.2 μm and a pore size of 50 nm.

[0052] The carboxyl content of lignin is 1.63 mmol / g, Hunan Taigelin Paper Group Co., Ltd.

[0053] The amino silane is γ-aminopropyltriethoxysilane.

[0054] The anion exchange resin is AG MP-1 anion exchange resin, chloride form, Bio-Rad Laboratories (Shanghai) Co., Ltd.

[0055] The cation exchange resin has a brand number of DOWEX50WX8, H form, Shanghai Kayin Chemical Co., Ltd.

[0056] The phosphorylated cation exchange resin: the mesh aperture is 150 meshes, and the pore size is 0.5 mm.

[0057] The size of the adsorption column: the diameter is 55 mm, the height is 150 mm, and 1 CV = 16 mL.

[0058] The silver powder model is 7440 - 22 - 4, the purity is 99.99%, produced by Thermo Fisher Scientific; the niobium powder model is Nb - 003, the purity is 99.99%, produced by Sem Biochemical Reagents (Shanghai) Co., Ltd.; the copper powder model is CU005140, the purity is 99.99%, produced by Gil Biochemical (Shanghai) Co., Ltd.

[0059] Example 1 A method for determining the composition of beryllium and aluminum isotopes in deep - sea ferromanganese nodules, comprising the following steps:

[0060] S1. Acid - extract the deep - sea ferromanganese nodules to obtain a test sample;

[0061] S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite ion - exchange resin, oscillate and adsorb for 20 - 30 min, after leaching with hydrochloric acid, collect the iron - element leachate, beryllium - element leachate, and aluminum - element leachate;

[0062] S3. Use inductively coupled plasma atomic emission spectrometry / mass spectrometry ICP - AES / MS to measure the concentrations of iron element, beryllium element, and aluminum element in the solution taken out in S1, and the concentrations of the iron - element leachate, beryllium - element leachate, and aluminum - element leachate taken out in S2;

[0063] S4. Add ammonia water to the iron - element leachate, beryllium - element leachate, and aluminum - element leachate respectively to adjust the pH value to 8.5, centrifuge to collect the precipitate, sinter the precipitate at 850 °C for 1 h to obtain oxides, mix and grind the oxides with silver powder, niobium powder, and copper powder respectively to obtain target samples, and place the target samples in the target disk of the accelerator mass spectrometer for determination;

[0064] Among them, in step S1, the specific steps of acid - extracting the deep - sea ferromanganese nodules are as follows:

[0065] Place 5 mg of deep - sea ferromanganese nodule sample in a 15 - mL centrifuge tube, add 5 mL of deionized water, 6 mL of hydrochloric acid with a concentration of 12 mol / L, and 1 mL of hydrogen peroxide, oscillate and react, soak overnight, and collect the supernatant a and residue a by centrifugation;

[0066] Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir well, soak overnight, and collect the supernatant b and residue b by centrifugation;

[0067] Place the residue b in 20 mL of deionized water, mix evenly, collect the supernatant c by centrifugation, mix the supernatant c, supernatant a, and supernatant b, evaporate until it becomes a curd-like state, then add 1 mL of hydrochloric acid with a concentration of 0.05 mol / L, collect the liquid, repeat this step 5 times, and collect the supernatant after centrifugation to obtain the test sample. Take 1 mL of the test sample solution, dilute it to 3 mL with deionized water, and measure the concentrations of iron, beryllium, and aluminum elements using an inductively coupled plasma optical / mass spectrometer ICP - AES / MS;

[0068] The specific operation of step S2 is as follows:

[0069] Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite ion exchange resin, oscillate and adsorb for 20 min, elute with hydrochloric acid with a concentration of 0.05 mol / L to 2.5 CV, collect the iron element eluate, elute with hydrochloric acid with a concentration of 0.5 mol / L to 6.5 CV, collect the beryllium element eluate, and elute with hydrochloric acid with a concentration of 2 mol / L to 10.5 CV, collect the aluminum element eluate;

[0070] The test sample, 9 Be carrier, 27 The mass ratio of the Al carrier is 4.6:0.5:0.5.

[0071] In step S4, the specific operation is as follows:

[0072] Mix the iron element eluate with ammonia water, adjust the pH to 8, collect the precipitate by centrifugation, sinter the precipitate at 850 °C for 1 h to obtain iron oxide, mix the iron oxide and silver powder, grind them to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0073] Mix the beryllium element eluate with ammonia water, adjust the pH to 8, collect the precipitate by centrifugation, sinter the precipitate at 850 °C for 1 h to obtain beryllium oxide, mix the beryllium oxide and silver, grind them to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0074] Mix the aluminum element eluate with ammonia water, adjust the pH to 8, collect the precipitate by centrifugation, sinter the precipitate at 850 °C for 1 h to obtain aluminum oxide, mix the aluminum oxide and niobium powder, grind them to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0075] The mass ratio of iron oxide and silver powder is 3:1;

[0076] The mass ratio of beryllium oxide and niobium powder is 3:1;

[0077] The mass ratio of aluminum oxide and copper powder is 5:1;

[0078] The composite exchange resin is specifically prepared by the following steps:

[0079] A1. Add 1.2 g of ferric chloride hexahydrate to 35 mL of deionized water, stir evenly, add 0.4 g of cetyltrimethylammonium bromide, 0.2 g of sodium hydroxide and 2 g of activated carbon, stir and mix at a rate of 500 r / min for 30 min, stir and react at 110 °C for 10 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 10 min to obtain activated carbon loaded with nano-iron oxide;

[0080] A2. Add 5.6 g of anion exchange resin to 20 mL of deionized water and 75 mL of ethanol, stir evenly, add 10 g of activated carbon loaded with nano-iron oxide and 0.5 g of γ-aminopropyltriethoxysilane, stir and mix at 60 °C for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain an iron ion adsorption material;

[0081] A3. After the cation exchange resin is crushed, ground and sieved, the sieve aperture is 110 mesh to obtain powdery resin particles. Add 1.6 g of powdery resin particles to 8 mL of deionized water and 25 mL of ethanol, stir evenly, add 0.2 g of 3-(trihydroxysilyl)propyl methyl phosphate, stir and react for 1 h, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain phosphorylated cation exchange resin;

[0082] A4. Mix 8 g of lignin and 90 mL of deionized water, stir evenly, add an aqueous sodium hydroxide solution with a mass fraction of 36% to adjust the pH to 10, add 1.2 g of oxalic acid, 3 g of phosphorylated cation exchange resin and 3 g of iron ion adsorption material, stir and mix at 50 °C for 10 min, cool to room temperature, stand overnight, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain the composite exchange resin.

[0083] Example 2 A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules, comprising the following steps:

[0084] S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample;

[0085] S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite exchange resin, oscillate and adsorb for 20 - 30 min, after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate;

[0086] S3. Use an inductively coupled plasma atomic emission spectrometer / mass spectrometer (ICP-AES / MS) to measure the concentrations of iron, beryllium, and aluminum elements in the solution taken out in S1, and the concentrations of the iron, beryllium, and aluminum element leachates taken out in S2;

[0087] S4. Add ammonia water to the iron, beryllium, and aluminum element leachates respectively to adjust the pH value to 8.5, centrifuge to collect the precipitate, sinter the precipitate at 900 °C for 1.5 h to obtain oxides, mix the oxides with silver powder, niobium powder, and copper powder respectively, grind them, obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for measurement;

[0088] Among them, in step S1, the specific steps for acid extraction of deep-sea ferromanganese nodules are as follows:

[0089] Place 5 mg of deep-sea ferromanganese nodule samples in a 15 mL centrifuge tube, add 5 mL of deionized water, 6 mL of hydrochloric acid with a concentration of 12 mol / L, and 1 mL of hydrogen peroxide, oscillate and react, soak overnight, and centrifuge to collect the supernatant a and the residue a;

[0090] Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir evenly, soak overnight, and centrifuge to collect the supernatant b and the residue b;

[0091] Place the residue b in 20 mL of deionized water, mix evenly, centrifuge to collect the supernatant c, mix the supernatant c, supernatant a, and supernatant b, evaporate to a curd-like state, then add 1 mL of hydrochloric acid with a concentration of 0.1 mol / L, collect the liquid, repeat this step 5 times, centrifuge and collect the supernatant to obtain the test sample. Take 1 mL of the test sample solution, dilute it to 3 mL with deionized water, and use an inductively coupled plasma optical / mass spectrometer (ICP-AES / MS) to measure the concentrations of iron, beryllium, and aluminum elements;

[0092] The specific operation of step S2 is as follows:

[0093] Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite ion exchange resin, oscillate and adsorb for 25 min, leach with hydrochloric acid with a concentration of 0.1 mol / L to 2.5 CV, collect the iron element leachate, leach with hydrochloric acid with a concentration of 1 mol / L to 6.5 CV, collect the beryllium element leachate, leach with hydrochloric acid with a concentration of 2.5 mol / L to 10.5 CV, and collect the aluminum element leachate;

[0094] The test sample, 9 Be carrier, 27 The mass ratio of the Al carrier is 4.6:0.5:0.5;

[0095] In step S4, the specific operation is as follows:

[0096] Mix the iron element leachate with ammonia water, adjust the pH to 8.5, centrifuge to collect the precipitate, sinter the precipitate at 800 °C for 1.5 h to obtain iron oxide, mix the iron oxide and silver powder, and after grinding, obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0097] Mix the beryllium element leachate with ammonia water, adjust the pH to 8.5, centrifuge to collect the precipitate, sinter the precipitate at 800 °C for 1.5 h to obtain beryllium oxide, mix the beryllium oxide and niobium powder, and after grinding, obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0098] Mix the aluminum element leachate with ammonia water, adjust the pH to 8.5, centrifuge to collect the precipitate, sinter the precipitate at 800 °C for 1.5 h to obtain aluminum oxide, mix the aluminum oxide and copper powder, and after grinding, obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0099] The mass ratio of iron oxide to silver powder is 3:1; the mass ratio of beryllium oxide to niobium powder is 3:1; the mass ratio of aluminum oxide to copper powder is 5:1.

[0100] The composite ion exchange resin is specifically prepared by the following steps:

[0101] A1. Add 1.3 g of ferric chloride hexahydrate to 40 mL of deionized water, stir evenly, add 0.5 g of cetyltrimethylammonium bromide, 0.3 g of sodium hydroxide, and 2.5 g of activated carbon, stir and mix at a rate of 550 r / min for 35 min, stir and react at 120 °C for 11 h, cool to room temperature, filter, wash 3 times with deionized water, and dry in an 80 °C oven for 10 min to obtain activated carbon loaded with nano-iron oxide;

[0102] A2. Add 5.7 g of anion exchange resin to 25 mL of deionized water and 80 mL of ethanol, stir evenly, add 10.5 g of activated carbon loaded with nano-iron oxide and 0.7 g of γ-aminopropyltriethoxysilane, stir and mix at 65 °C for 3 h, filter, wash 3 times with deionized water, and dry in a 70 °C oven for 10 min to obtain an iron ion adsorbent material;

[0103] A3. After the cation exchange resin is crushed, ground, and sieved, the sieve aperture is 130 mesh to obtain powdery resin particles. Add 1.7 g of powdery resin particles to 10 mL of deionized water and 30 mL of ethanol, stir evenly, add 0.3 g of 3-(trihydroxysilyl)propylmethyl phosphate, stir and react for 1.5 h, filter, wash 3 times with deionized water, and dry in a 50 °C oven for 10 min to obtain phosphorylated cation exchange resin;

[0104] A4. Mix 10 g of lignin with 100 mL of deionized water, stir evenly, add an aqueous sodium hydroxide solution with a mass fraction of 36% to adjust the pH to 10.5, add 1.3 g of oxalic acid, 3.5 g of phosphorylated cation exchange resin, and 3.3 g of iron ion adsorbent material, stir and mix at 55 °C for 15 min, cool to room temperature, let stand overnight, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain the composite exchange resin.

[0105] Example 3 A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules, comprising the following steps:

[0106] S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample;

[0107] S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with the composite exchange resin, oscillate and adsorb for 20 - 30 min, after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate;

[0108] S3. Use an inductively coupled plasma optical emission spectrometry / mass spectrometry (ICP-AES / MS) to measure the concentrations of iron element, beryllium element, and aluminum element in the solution taken out in S1, and the concentrations of the iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2;

[0109] S4. Add ammonia water to the iron element leachate, beryllium element leachate, and aluminum element leachate respectively to adjust the pH value to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain oxides, mix the oxides with silver powder, niobium powder, and copper powder respectively, grind them to obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for determination;

[0110] Among them, in step S1, the specific steps of acid-extracting the deep-sea ferromanganese nodules are as follows:

[0111] Place 5 mg of deep-sea ferromanganese nodule sample in a 15 mL centrifuge tube, add 5 mL of deionized water, 6 mL of hydrochloric acid with a concentration of 12 mol / L, and 1 mL of hydrogen peroxide, oscillate and react, soak overnight, and centrifuge to collect the supernatant a and the residue a;

[0112] Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir evenly, soak overnight, and centrifuge to collect the supernatant b and the residue b;

[0113] Place the residue b in 20 mL of deionized water, mix evenly, collect the supernatant c by centrifugation, mix the supernatant c, supernatant a, and supernatant b, evaporate to a curd-like state, then add 1 mL of hydrochloric acid with a concentration of 0.15 mol / L, collect the liquid, repeat this step 5 times, and collect the supernatant after centrifugation to obtain the test sample. Take 1 mL of the test sample solution, dilute it to 3 mL with deionized water, and measure the concentrations of iron, beryllium, and aluminum elements using an inductively coupled plasma optical / mass spectrometer ICP - AES / MS;

[0114] The specific operation of step S2 is as follows:

[0115] Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite ion exchange resin, oscillate and adsorb for 30 min, elute with hydrochloric acid with a concentration of 0.075 mol / L to 2.5 CV, collect the iron element eluate, elute with hydrochloric acid with a concentration of 0.75 mol / L to 6.5 CV, collect the beryllium element eluate, and elute with hydrochloric acid with a concentration of 3 mol / L to 10.5 CV, collect the aluminum element eluate;

[0116] The test sample, 9 Be carrier, 27 The mass ratio of the Al carrier is 4.6:0.5:0.5.

[0117] In step S4, the specific operation is as follows:

[0118] Mix the iron element eluate with ammonia water, adjust the pH to 9, collect the precipitate by centrifugation, sinter the precipitate at 950 °C for 2 h to obtain iron oxide, mix the iron oxide and silver powder, grind them to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0119] Mix the beryllium element eluate with ammonia water, adjust the pH to 9, collect the precipitate by centrifugation, sinter the precipitate at 950 °C for 2 h to obtain beryllium oxide, mix the beryllium oxide and niobium powder, grind them to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0120] Mix the aluminum element eluate with ammonia water, adjust the pH to 9, collect the precipitate by centrifugation, sinter the precipitate at 950 °C for 2 h to obtain aluminum oxide, mix the aluminum oxide and copper powder, grind them to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0121] The mass ratio of iron oxide and silver powder is 3:1; the mass ratio of beryllium oxide and niobium powder is 3:1; the mass ratio of aluminum oxide and copper powder is 5:1.

[0122] The composite ion exchange resin is specifically prepared by the following steps:

[0123] A1. Add 1.4 g of ferric chloride hexahydrate to 45 mL of deionized water, stir evenly, add 0.6 g of cetyltrimethylammonium bromide, 0.4 g of sodium hydroxide and 3 g of activated carbon, stir and mix at a rate of 600 r / min for 40 min, stir and react at 130 °C for 12 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 10 min to obtain activated carbon loaded with nano-iron oxide;

[0124] A2. Add 5.8 g of anion exchange resin to 30 mL of deionized water and 85 mL of ethanol, stir evenly, add 10.5 g of activated carbon loaded with nano-iron oxide and 0.7 g of γ-aminopropyltriethoxysilane, stir and mix at 70 °C for 5 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain an iron ion adsorption material;

[0125] A3. After the cation exchange resin is crushed, ground and sieved, the sieve aperture is 150 mesh to obtain powdery resin particles. Add 1.8 g of powdery resin particles to 12 mL of deionized water and 35 mL of ethanol, stir evenly, add 0.4 g of 3-(trihydroxysilyl)propyl methyl phosphate, stir and react for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain phosphorylated cation exchange resin;

[0126] A4. Mix 12 g of lignin and 120 mL of deionized water, stir evenly, add an aqueous sodium hydroxide solution with a mass fraction of 36% to adjust the pH to 11, add 1.4 g of oxalic acid, 4 g of phosphorylated cation exchange resin and 3.6 g of iron ion adsorption material, stir and mix at 60 °C for 20 min, cool to room temperature, stand overnight, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain a composite exchange resin.

[0127] Comparative Example 1

[0128] A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules includes the following steps:

[0129] S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample;

[0130] S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite exchange resin, oscillate and adsorb for 20 - 30 min, after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate;

[0131] S3. Use inductively coupled plasma atomic emission spectrometry / mass spectrometry (ICP-AES / MS) to measure the concentrations of iron, beryllium, and aluminum elements in the solution taken out in S1, and the concentrations of the leachates of iron, beryllium, and aluminum elements taken out in S2;

[0132] S4. Add ammonia water to the leachates of iron, beryllium, and aluminum elements respectively to adjust the pH value to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain oxides, mix the oxides with silver powder, niobium powder, and copper powder respectively, grind them to obtain target samples, and place the target samples in the target disk of the accelerator mass spectrometer for determination;

[0133] Among them, in step S1, the specific steps for acid extraction of deep-sea ferromanganese nodules are as follows:

[0134] Place 5 mg of deep-sea ferromanganese nodule samples in a 15 mL centrifuge tube, add 5 mL of deionized water, 6 mL of hydrochloric acid with a concentration of 12 mol / L, and 1 mL of hydrogen peroxide. After oscillating and reacting, soak overnight, and centrifuge to collect the supernatant a and the residue a;

[0135] Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir well, soak overnight, and centrifuge to collect the supernatant b and the residue b;

[0136] Place the residue b in 20 mL of deionized water, mix evenly, centrifuge to collect the supernatant c, mix the supernatant c, supernatant a, and supernatant b, evaporate to a curd-like state, then add 1 mL of hydrochloric acid with a concentration of 0.15 mol / L, collect the liquid, repeat this step 5 times, centrifuge and collect the supernatant to obtain the test sample. Take 1 mL of the test sample solution, dilute it to 3 mL with deionized water, and use inductively coupled plasma optical / mass spectrometry (ICP-AES / MS) to measure the concentrations of iron, beryllium, and aluminum elements;

[0137] The specific operation of step S2 is as follows:

[0138] Transfer the test sample, 9 Be carrier, 27 Al carrier into the adsorption column filled with composite ion exchange resin, oscillate and adsorb for 30 min, leach with hydrochloric acid with a concentration of 0.1 mol / L to 2.5 CV, collect the iron element leachate, leach with hydrochloric acid with a concentration of 1.0 mol / L to 6.5 CV, collect the beryllium element leachate, and leach with hydrochloric acid with a concentration of 2.5 mol / L to 10.5 CV, collect the aluminum element leachate;

[0139] The test sample, 9 Be carrier, 27 The mass ratio of the Al carrier is 4.6:0.5:0.5.

[0140] In step S4, the specific operation is as follows:

[0141] Mix the iron element leaching solution with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain iron oxide, mix the iron oxide and silver powder, and after grinding, obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0142] Mix the beryllium element leaching solution with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain beryllium oxide, mix the beryllium oxide and niobium powder, and after grinding, obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0143] Mix the aluminum element leaching solution with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain aluminum oxide, mix the aluminum oxide and copper powder, and after grinding, obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0144] The mass ratio of iron oxide to silver powder is 3:1; the mass ratio of beryllium oxide to niobium powder is 3:1; the mass ratio of aluminum oxide to copper powder is 5:1.

[0145] The composite ion exchange resin is specifically prepared by the following steps:

[0146] A1. Add 5.8 g of anion exchange resin to 30 mL of deionized water and 85 mL of ethanol, stir evenly, add 10.5 g of activated carbon and 0.7 g of γ-aminopropyltriethoxysilane, stir and mix at 70 °C for 5 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain an iron ion adsorption material;

[0147] A2. After the cation exchange resin is crushed, ground, and sieved, the sieve aperture is 150 mesh to obtain powdery resin particles. Add 1.8 g of powdery resin particles to 12 mL of deionized water and 35 mL of ethanol, stir evenly, add 0.4 g of 3-(trihydroxysilyl)propyl methyl phosphate, stir and react for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain phosphorylated cation exchange resin;

[0148] A3. Mix 12 g of lignin and 120 mL of deionized water, stir evenly, add an aqueous sodium hydroxide solution with a mass fraction of 36% to adjust the pH to 11, add 1.4 g of oxalic acid, 4 g of phosphorylated cation exchange resin, and 3.6 g of iron ion adsorption material, stir and mix at 60 °C for 20 min, cool to room temperature, stand overnight, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain the composite ion exchange resin.

[0149] Comparative Example 2

[0150] Method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules, comprising the following steps:

[0151] S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample;

[0152] S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with a composite ion-exchange resin, oscillate and adsorb for 20 - 30 min, after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate;

[0153] S3. Use an inductively coupled plasma atomic emission spectrometer / mass spectrometer ICP-AES / MS to measure the concentrations of iron element, beryllium element, and aluminum element in the solution taken out in S1, and the concentrations of the iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2;

[0154] S4. Add ammonia water to the iron element leachate, beryllium element leachate, and aluminum element leachate respectively to adjust the pH value to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain oxides, mix the oxides with silver powder, niobium powder, and copper powder respectively, grind them to obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for determination;

[0155] Among them, in step S1, the specific steps of acid-extracting the deep-sea ferromanganese nodules are as follows:

[0156] Place 5 mg of deep-sea ferromanganese nodule sample in a 15 mL centrifuge tube, add 5 mL of deionized water, 6 mL of hydrochloric acid with a concentration of 12 mol / L, and 1 mL of hydrogen peroxide, oscillate and react, soak overnight, and collect the supernatant a and residue a by centrifugation;

[0157] Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir evenly, soak overnight, and collect the supernatant b and residue b by centrifugation;

[0158] Place the residue b in 20 mL of deionized water, mix evenly, collect the supernatant c by centrifugation, mix the supernatant c, supernatant a, and supernatant b, evaporate to a curd-like state, then add 1 mL of hydrochloric acid with a concentration of 0.15 mol / L, collect the liquid, repeat this step 5 times, and collect the supernatant by centrifugation to obtain a test sample. Take 1 mL of the test sample solution, dilute it to 3 mL with deionized water, and use an inductively coupled plasma optical / mass spectrometer ICP-AES / MS to measure the concentrations of iron element, beryllium element, and aluminum element;

[0159] The specific operation of step S2 is as follows:

[0160] Transfer the test sample, 9 Be carrier, 27Transfer the Al carrier into an adsorption column filled with composite ion-exchange resin, shake and adsorb for 30 min, elute with 0.1 mol / L hydrochloric acid to 2.5 CV, collect the iron element eluate, elute with 1.0 mol / L hydrochloric acid to 6.5 CV, collect the beryllium element eluate, and elute with 2.5 mol / L hydrochloric acid to 10.5 CV, collect the aluminum element eluate;

[0161] Test sample, 9 Be carrier, 27 The mass ratio of the Fe carrier, Be carrier, and Al carrier is 4.6:0.5:0.5.

[0162] In step S4, the specific operation is as follows:

[0163] Mix the iron element eluate with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain iron oxide, mix the iron oxide and silver powder, grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0164] Mix the beryllium element eluate with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain beryllium oxide, mix the beryllium oxide and niobium powder, grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0165] Mix the aluminum element eluate with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain aluminum oxide, mix the aluminum oxide and copper powder, grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination;

[0166] The mass ratio of iron oxide to silver powder is 3:1; the mass ratio of beryllium oxide to niobium powder is 3:1; the mass ratio of aluminum oxide to copper powder is 5:1.

[0167] The composite ion-exchange resin is specifically prepared by the following steps:

[0168] A1. Add 1.4 g of ferric chloride hexahydrate to 45 mL of deionized water, stir evenly, add 0.6 g of cetyltrimethylammonium bromide, 0.4 g of sodium hydroxide, and 3 g of activated carbon, stir and mix at a rate of 600 r / min for 40 min, stir and react at 130 °C for 12 h, cool to room temperature, filter, wash 3 times with deionized water, and dry in an 80 °C oven for 10 min to obtain activated carbon loaded with nano-iron oxide;

[0169] A2. Add 5.8 g of anion exchange resin to 30 mL of deionized water and 85 mL of ethanol, stir evenly, add 10.5 g of activated carbon loaded with nano-iron oxide and 0.7 g of methyltrimethoxysilane, stir and mix at 70 °C for 5 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain an iron ion adsorption material;

[0170] A3. After the cation exchange resin is crushed, ground, and sieved, the sieve aperture is 150 mesh to obtain powdery resin particles. Add 1.8 g of powdery resin particles to 12 mL of deionized water and 35 mL of ethanol, stir evenly, add 0.4 g of 3-(trihydroxysilyl)propyl methyl phosphate, stir and react for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain phosphorylated cation exchange resin;

[0171] A4. Mix 12 g of lignin and 120 mL of deionized water, stir evenly, add an aqueous sodium hydroxide solution with a mass fraction of 36% to adjust the pH to 11, add 1.4 g of oxalic acid, 4 g of phosphorylated cation exchange resin, and 3.6 g of iron ion adsorption material, stir and mix at 60 °C for 20 min, cool to room temperature, stand overnight, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain a composite exchange resin.

[0172] Comparative Example 3

[0173] A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules, comprising the following steps:

[0174] S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample;

[0175] S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite exchange resin, oscillate and adsorb for 20 - 30 min, after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate;

[0176] S3. Use inductively coupled plasma spectroscopy / mass spectrometry ICP - AES / MS to measure the concentrations of iron element, beryllium element, and aluminum element in the solution taken out in S1, and the concentrations of partial iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2;

[0177] S4. Add ammonia water to the iron element leachate, beryllium element leachate, and aluminum element leachate respectively to adjust the pH value to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain oxides, mix the oxides with silver powder, niobium powder, and copper powder respectively, grind them to obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for determination;

[0178] Among them, in step S1, the specific steps for acid extraction of deep-sea ferromanganese nodules are as follows:

[0179] Place 5 mg of deep-sea ferromanganese nodule sample in a 15 mL centrifuge tube, add 5 mL of deionized water, 6 mL of hydrochloric acid with a concentration of 12 mol / L, and 1 mL of hydrogen peroxide. After oscillating and reacting, soak overnight, and collect the supernatant a and residue a by centrifugation;

[0180] Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir well, soak overnight, and collect the supernatant b and residue b by centrifugation;

[0181] Place the residue b in 20 mL of deionized water, mix evenly, collect the supernatant c by centrifugation, mix the supernatant c, supernatant a, and supernatant b, evaporate to a curd-like state, then add 1 mL of hydrochloric acid with a concentration of 0.15 mol / L, collect the liquid, repeat this step 5 times, and collect the supernatant after centrifugation to obtain the test sample. Take 1 mL of the test sample solution, dilute it to 3 mL with deionized water, and measure the concentrations of iron element, beryllium element, and aluminum element with an inductively coupled plasma optical / mass spectrometer ICP-AES / MS;

[0182] The specific operation of step S2 is as follows:

[0183] Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite ion exchange resin, oscillate and adsorb for 30 min, elute with hydrochloric acid with a concentration of 0.1 mol / L to 2.5 CV, collect the iron element eluate, elute with hydrochloric acid with a concentration of 1.0 mol / L to 6.5 CV, collect the beryllium element eluate, and elute with hydrochloric acid with a concentration of 2.5 mol / L to 10.5 CV, collect the aluminum element eluate;

[0184] Test sample, 9 Be carrier, 27 The mass ratio of the Al carrier is 4.6:0.5:0.5.

[0185] In step S4, the specific operation is as follows:

[0186] Mix the iron element eluate with ammonia water, adjust the pH to 9, collect the precipitate by centrifugation, sinter the precipitate at 950 °C for 2 h to obtain iron oxide, mix the iron oxide and silver powder, grind to obtain the target sample, and place the target sample in the target disk of the accelerator mass spectrometer for determination;

[0187] Mix the beryllium element eluate with ammonia water, adjust the pH to 9, collect the precipitate by centrifugation, sinter the precipitate at 950 °C for 2 h to obtain beryllium oxide, mix the beryllium oxide and niobium powder, grind to obtain the target sample, and place the target sample in the target disk of the accelerator mass spectrometer for determination;

[0188] Mix the aluminum leachate with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain alumina, mix the alumina and copper powder, and grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0189] The mass ratio of iron oxide to silver powder is 3:1; the mass ratio of beryllium oxide to niobium powder is 3:1; the mass ratio of alumina to copper powder is 5:1.

[0190] The composite ion exchange resin is specifically prepared by the following steps:

[0191] A1. Add 1.4 g of ferric chloride hexahydrate to 45 mL of deionized water, stir evenly, add 0.6 g of cetyltrimethylammonium bromide, 0.4 g of sodium hydroxide and 3 g of activated carbon, stir and mix at a rate of 600 r / min for 40 min, stir and react at 130 °C for 12 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 10 min to obtain activated carbon loaded with nano-iron oxide;

[0192] A2. Add 5.8 g of anion exchange resin to 30 mL of deionized water and 85 mL of ethanol, stir evenly, add 10.5 g of activated carbon loaded with nano-iron oxide and 0.7 g of γ-aminopropyltriethoxysilane, stir and mix at 70 °C for 5 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain an iron ion adsorbent material;

[0193] A3. After the cation exchange resin is crushed, ground and sieved, the mesh aperture of the sieve is 150 meshes to obtain powdery resin particles;

[0194] A4. Mix 12 g of lignin and 120 mL of deionized water, stir evenly, add an aqueous sodium hydroxide solution with a mass fraction of 36% to adjust the pH to 11, add 1.4 g of oxalic acid, 4 g of powdery resin particles and 3.6 g of iron ion adsorbent material, stir and mix at 60 °C for 20 min, cool to room temperature, stand overnight, filter, wash with deionized water 3 times, and dry in an oven at 50 °C for 10 min to obtain the composite ion exchange resin.

[0195] Comparative Example 4

[0196] A method for determining the beryllium and aluminum isotope composition in deep-sea ferromanganese nodules, comprising the following steps:

[0197] S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample;

[0198] S2. The test sample, 9 Be carrier, 27Transfer the Al carrier into an adsorption column filled with composite ion-exchange resin, shake and adsorb for 20 - 30 min, and after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate;

[0199] S3. Use inductively coupled plasma atomic emission spectrometry / mass spectrometry (ICP - AES / MS) to measure the concentrations of iron element, beryllium element, and aluminum element in the solution taken out in S1, and the concentrations of the iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2;

[0200] S4. Add ammonia water to the iron element leachate, beryllium element leachate, and aluminum element leachate respectively to adjust the pH value to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain oxides, mix the oxides with silver powder, niobium powder, and copper powder respectively, grind them, and then obtain target samples. Put the target samples into the target disk of an accelerator mass spectrometer for determination;

[0201] Among them, in step S1, the specific steps for acid extraction of deep - sea ferromanganese nodules are as follows:

[0202] Place 5 mg of deep - sea ferromanganese nodule samples in a 15 - mL centrifuge tube, add 5 mL of deionized water, 6 mL of hydrochloric acid with a concentration of 12 mol / L, and 1 mL of hydrogen peroxide. After shaking and reacting, soak overnight, and centrifuge to collect the supernatant a and the residue a;

[0203] Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir well, soak overnight, and centrifuge to collect the supernatant b and the residue b;

[0204] Place the residue b in 20 mL of deionized water, mix evenly, centrifuge to collect the supernatant c, mix the supernatant c, supernatant a, and supernatant b, evaporate to a curd - like state, then add 1 mL of hydrochloric acid with a concentration of 0.15 mol / L, collect the liquid, repeat this step 5 times, and centrifuge to collect the supernatant to obtain the test sample. Take 1 mL of the test sample solution, dilute it to 3 mL with deionized water, and use inductively coupled plasma optical / mass spectrometry (ICP - AES / MS) to measure the concentrations of iron element, beryllium element, and aluminum element;

[0205] The specific operation of step S2 is as follows:

[0206] Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite ion - exchange resin, shake and adsorb for 30 min, leach with 0.1 mol / L hydrochloric acid to 2.5 CV, collect the iron element leachate, leach with 1.0 mol / L hydrochloric acid to 6.5 CV, collect the beryllium element leachate, leach with 2.5 mol / L hydrochloric acid to 10.5 CV, and collect the aluminum element leachate;

[0207] Test sample, 9 Be carrier, 27 The mass ratio of the Al carrier is 4.6:0.5:0.5.

[0208] In step S4, the specific operation is as follows:

[0209] Mix the iron element leaching solution with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain iron oxide, mix the iron oxide and silver powder, grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0210] Mix the beryllium element leaching solution with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain beryllium oxide, mix the beryllium oxide and niobium powder, grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0211] Mix the aluminum element leaching solution with ammonia water, adjust the pH to 9, centrifuge to collect the precipitate, sinter the precipitate at 950 °C for 2 h to obtain aluminum oxide, mix the aluminum oxide and copper powder, grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for measurement;

[0212] The mass ratio of iron oxide to silver powder is 3:1; the mass ratio of beryllium oxide to niobium powder is 3:1; the mass ratio of aluminum oxide to copper powder is 5:1.

[0213] The composite ion exchange resin is specifically prepared by the following steps:

[0214] A1. Add 1.4 g of ferric chloride hexahydrate to 45 mL of deionized water, stir evenly, add 0.6 g of cetyltrimethylammonium bromide, 0.4 g of sodium hydroxide and 3 g of activated carbon, stir and mix at a rate of 600 r / min for 40 min, stir and react at 130 °C for 12 h, cool to room temperature, filter, wash 3 times with deionized water, and dry in an oven at 80 °C for 10 min to obtain activated carbon loaded with nano-iron oxide;

[0215] A2. Add 5.8 g of anion exchange resin to 30 mL of deionized water and 85 mL of ethanol, stir evenly, add 10.5 g of activated carbon loaded with nano-iron oxide and 0.7 g of γ-aminopropyltriethoxysilane, stir and mix at 70 °C for 5 h, filter, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain an iron ion adsorption material;

[0216] A3. After the cation exchange resin is crushed, ground, and sieved through a sieve with a pore size of 150 mesh, powdery resin particles are obtained. 1.8 g of the powdery resin particles are added to 12 mL of deionized water and 35 mL of ethanol, stirred evenly, 0.4 g of 3-(trihydroxysilyl)propylmethyl phosphate is added, and the mixture is stirred and reacted for 2 h. After filtration, it is washed 3 times with deionized water and dried in an oven at 50 °C for 10 min to obtain phosphorylated cation exchange resin;

[0217] A4. 4 g of the phosphorylated cation exchange resin and 3.6 g of the iron ion adsorbent are mixed to obtain a composite exchange resin.

[0218] Now, a method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules of Examples 1-3 and Comparative Examples 1-4 is detected.

[0219] The iron concentration in the above test sample is 31 mg / L, the beryllium concentration is 15 mg / L, and the aluminum concentration is 27 mg / L.

[0220] The concentrations (mg / L) of the iron element leachate, beryllium element leachate, and aluminum element leachate are measured using an inductively coupled plasma optical emission spectrometry / mass spectrometry ICP-AES / MS to represent the adsorption effect and extraction effect.

[0221] Iron oxide and silver powder are mixed, beryllium oxide and niobium powder are mixed, and aluminum oxide and copper powder are mixed. They are respectively ground and placed in the target disk of an accelerator mass spectrometer to measure the ratio, and the composition of iron isotopes cannot be detected.

[0222] The test results are shown in Tables 1 and 2 below.

[0223] Table 1 Leaching results in Examples 1-3 and Comparative Examples 1-4

[0224]

[0225] Table 2 Measured isotope ratios in Examples 1-3 and Comparative Examples 1-4

[0226]

[0227] It can be seen from the data in Tables 1 and 2 that the method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules of Examples 1-3 has a high recovery rate and a small detection error.

[0228] In Comparative Example 1, the composite exchange resin prepared by replacing the activated carbon loaded with nano iron oxide with activated carbon was used for the extraction and detection of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules. The extraction effect decreased and the detection error was large, which proved that nano iron oxide was synthesized in the pores of activated carbon, and the hydroxyl groups carried on the surface of nano iron oxide could adsorb iron ions directionally, reducing the interference of other metal ions and improving the extraction efficiency. In addition, it avoided the adsorption of impurity metals into the adsorption column filled with the composite exchange resin, resulting in impure collected metal isotopes and affecting the detection effect.

[0229] In Comparative Example 2, the composite exchange resin prepared by replacing γ-aminopropyltriethoxysilane with methyltrimethoxysilane was used for the extraction and detection of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules. The extraction effect decreased and the detection error was large, which proved that the anion exchange resin was adsorbed on the surface of the activated carbon loaded with nano iron oxide through aminosilane. The iron element in the ferromanganese nodule test sample could exchange with the anion group in the anion exchange resin, enabling the iron element to be adsorbed into the iron ion adsorption material, and the compounded and directionally adsorbed nano iron oxide improved the extraction efficiency and reduced the detection error.

[0230] In Comparative Example 3, the composite exchange resin prepared by replacing the phosphorylated cation exchange resin with powdered resin particles was used for the extraction and detection of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules. The extraction effect decreased and the detection error was large, which proved that 3-(trihydroxysilyl)propylmethyl phosphate was grafted onto the cation exchange resin, introducing phosphate groups onto the porous cation exchange resin. The phosphate groups could complex with the aluminum element in the ferromanganese nodule test sample to form specific adsorption, completing the adsorption performance of the aluminum element, and the contained phosphate groups could form a stable complex with the beryllium element through beryllium-oxygen-phosphorus to complete the directional adsorption of the beryllium element.

[0231] In Comparative Example 4, the composite exchange resin prepared without adding lignin and oxalic acid was used for the extraction and detection of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules. The extraction effect decreased and the detection error was large, which proved that the phosphorylated cation exchange resin, iron ion adsorption material, oxalic acid, and lignin were mixed and reacted to form a composite exchange resin with a crosslinked porous structure and filled into the adsorption column, which could simultaneously extract the three isotopes of iron, beryllium, and aluminum in the ferromanganese nodules, reducing the sample demand and the deviation introduced by the analysis of multiple samples. Moreover, the porous structure had excellent adsorption performance for metal ions, improving the extraction rate of iron element, aluminum element, and beryllium element in the ferromanganese nodule test sample.

[0232] In the description of the specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0233] The above content is only an example and illustration of the present invention. Those skilled in the art to which the present technology pertains can make various modifications or supplements to the described specific embodiments or use similar ways to substitute them, as long as they do not deviate from the scope defined by the invention, they should all fall within the protection scope of the present invention.

Claims

1. A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules, characterized in that, It includes the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain test samples; take the test samples and measure the original concentrations of iron, beryllium, and aluminum elements using an inductively coupled plasma optical / mass spectrometer ICP-AES / MS; S2. Add 9 the Be support, 27 the Al support to the test sample, then transfer it into an adsorption column filled with a composite ion exchange resin, oscillate and adsorb for 20 - 30 min, after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate; S3. Take the eluents of iron, beryllium, and aluminum elements and measure the concentrations of the iron element eluate, beryllium element eluate, and aluminum element eluate using an inductively coupled plasma optical / mass spectrometer ICP-AES / MS to test the process recovery rate; S4. Add ammonia water to the iron element eluate, beryllium element eluate, and aluminum element eluate respectively to adjust the pH value to 8-9, centrifuge to collect the precipitate, sinter the precipitate at 850-950 °C for 1-2 h to obtain oxides, mix the oxides with silver powder, niobium powder, and copper powder respectively, grind them, obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for determination; The composite ion exchange resin is specifically prepared by the following steps: A1. Add ferric chloride hexahydrate to deionized water, stir evenly, add cetyltrimethylammonium bromide, sodium hydroxide, and activated carbon, stir and mix at a rate of 500-600 r / min for 30-40 min, stir and react at 110-130 °C for 10-12 h, cool to room temperature, filter, wash, and dry to obtain activated carbon loaded with nano-iron oxide; A2. Add an anion exchange resin to deionized water and ethanol, stir evenly, add activated carbon loaded with nano-iron oxide and γ-aminopropyltriethoxysilane, stir and mix at 60-70 °C for 2-5 h, filter, wash, and dry to obtain an iron ion adsorption material; A3. After the cation exchange resin is crushed, ground, and sieved, the mesh aperture of the sieve is 110-150 mesh to obtain powdery resin particles. Add the powdery resin particles to deionized water and ethanol, stir evenly, add 3-(trihydroxysilyl)propylmethylphosphonate, stir and react for 1-2 h, filter, wash, and dry to obtain phosphorylated cation exchange resin; A4. Mix lignin and deionized water, stir evenly, add an aqueous sodium hydroxide solution to adjust the pH to 10-11, add oxalic acid, phosphorylated cation exchange resin, and iron ion adsorption material, stir and mix at 50-60 °C for 10-20 min, cool to room temperature, stand overnight, filter, wash, and dry to obtain the composite ion exchange resin.

2. The method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that, In step A1, the dosage ratio of ferric chloride hexahydrate, deionized water, cetyltrimethylammonium bromide, sodium hydroxide, and activated carbon is (1.2-1.4) g:(35-45) mL:(0.4-0.6) g:(0.2-0.4) g:(2-3) g.

3. A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that, In step A2, the mass ratio of the anion exchange resin, deionized water, ethanol, activated carbon loaded with nano-iron oxide, and γ-aminopropyltriethoxysilane is (5.6-5.8) g:(20-30) mL:(75-85) mL:(10-11) g:(0.5-0.9) g.

4. The method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that, In step A3, the dosage ratio of the powdery resin particles, deionized water, ethanol, and 3-(trihydroxysilyl)propylmethylphosphonate is (1.6 - 1.8) g : (8 - 12) mL : (25 - 35) mL : (0.2 - 0.4) g.

5. The method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that, In step A4, the dosage ratio of the lignin, deionized water, oxalic acid, phosphorylated cation exchange resin, and iron ion adsorbent is (8 - 12) g : (90 - 120) mL : (1.2 - 1.4) g : (3 - 4) g : (3 - 3.6) g.

6. A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that, In step S1, the specific steps for acid extraction of the deep-sea ferromanganese nodules are as follows: Place the deep-sea ferromanganese nodule sample in a centrifuge tube, add deionized water, hydrochloric acid, and hydrogen peroxide. After oscillating and reacting, soak overnight, and collect the supernatant a and residue a by centrifugation; Add hydrochloric acid to the residue a, stir well, soak overnight, and collect the supernatant b and residue b by centrifugation; Place the residue b in deionized water, mix evenly, collect the supernatant c by centrifugation, mix the supernatant c, supernatant a, and supernatant b, evaporate to a curd-like state, then add hydrochloric acid to dissolve and collect the solution. Repeat the dissolution 5 times, collect the supernatant after centrifugation to obtain a test sample. Take the test sample and measure the original concentrations of iron element, beryllium element, and aluminum element using an inductively coupled plasma optical / mass spectrometer ICP-AES / MS.

7. A method for determining the composition of beryllium and aluminum isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that, The specific operation of step S2 is as follows: 9 The Be carrier, 27 The Al carrier are added to the test sample and then transferred into an adsorption column filled with a composite ion-exchange resin, shaken for adsorption for 20 - 30 min, leached with hydrochloric acid with a concentration of 0.05 - 0.01 mol / L to 1 - 2.5 CV, the iron element leachate is collected, leached with hydrochloric acid with a concentration of 0.5 - 1.0 mol / L to 4.5 - 6.5 CV, the beryllium element leachate is collected, leached with hydrochloric acid with a concentration of 2 - 3 mol / L to 8.5 - 10.5 CV, and the aluminum element leachate is collected.

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