Method for determining composition of beryllium, aluminum and iron isotopes in deep sea iron manganese nodule

Abstract

The invention relates to the technical field of isotope determination, and discloses a method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea iron-manganese nodules, which comprises the following steps: performing acid extraction on deep-sea iron-manganese nodules to obtain a test sample; the method comprises the following steps: adding a 9Be carrier and a 27Al carrier into a test sample, transferring into an adsorption column filled with composite exchange resin, oscillating and adsorbing, leaching with hydrochloric acid, and collecting an iron element leaching solution, a beryllium element leaching solution and an aluminum element leaching solution; measuring the concentrations of the iron element leachate, the beryllium element leachate and the aluminum element leachate by using a plasma mass spectrometer; respectively adding ammonia water into the iron element leachate, the beryllium element leachate and the aluminum element leachate, centrifugally collecting precipitates, sintering the precipitates to obtain an oxide, respectively mixing the oxide with silver powder, niobium powder and copper powder, grinding to obtain a target sample, and placing the target sample into a target disc 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, aluminum, and iron isotopes in deep-sea ferromanganese nodules. Background Art

[0002] Polymetallic nodules in the ocean are polymetallic ore deposits that grow on the deep seabed. Also known as deep-sea manganese nodules, manganese ore balls, manganese ore nodules, or manganese nodules, they mainly consist of oxides and hydroxides of manganese and iron, contain various metal elements such as copper, nickel, and cobalt, and mostly exist in nodular form. 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] Beryllium in deep-sea ferromanganese nodules exists as Be 2+ ; aluminum exists as Al 3+ ; 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, when using ion exchange resins, other impurity metals will be adsorbed, and the directional adsorption property is poor, resulting in impurity metals being adsorbed into the adsorption column filled with composite exchange resin, and the collected metal isotopes being impure, which affects the detection effect. Summary of the Invention

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

[0005] The technical solution of the present invention is as follows: A method for determining the compositions of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules, comprising the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; S2. Transfer the test sample, 9 Be carrier, 27 and Al carrier into an adsorption column filled with composite exchange resin, oscillate and adsorb for 20 - 30 minutes, then perform leaching with hydrochloric acid, and collect the iron element leachate, beryllium element leachate, and aluminum element leachate; S3. Use an inductively coupled plasma optical 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; S4. Add ammonia water to the leachate of iron element, beryllium element, and aluminum element 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 to obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for measurement; The composite ion exchange resin is obtained by mixing and reacting phosphorylated cation exchange resin, iron element adsorbent material, oxalic acid, and lignin; 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; The phosphorylated cation exchange resin is obtained by crushing, grinding, and sieving cation exchange resin, and then mixing and reacting with 3-(trihydroxysilyl)propyl methyl phosphate.

[0006] Further, in step S1, the specific steps for acid extraction of 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, oscillate and react, soak overnight, and centrifuge to collect supernatant a and residue a; Add hydrochloric acid to residue a, stir evenly, soak overnight, and centrifuge to collect supernatant b and residue b; 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: 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, leach with hydrochloric acid with a concentration of 0.05 - 0.1 mol / L to 1 - 2.5 CV, collect the leachate of iron element, leach with hydrochloric acid with a concentration of 0.5 - 1.0 mol / L to 4.5 - 6.5 CV, collect the leachate of beryllium element, leach with hydrochloric acid with a concentration of 2 - 3 mol / L to 8.5 - 10.5 CV, and collect the leachate of aluminum element.

[0007] Further, the mass ratio of the test sample, 9 Be carrier, 27 Al carrier is 4.6:0.5:0.5.

[0008] Further, in step S4, the specific operation is as follows: Mix the iron leachate 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; Mix the beryllium leachate 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; Mix the aluminum leachate 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.

[0009] Furthermore, the mass ratio of iron oxide to silver powder is 3:1.

[0010] Furthermore, the mass ratio of beryllium oxide to niobium powder is 3:1.

[0011] Furthermore, the mass ratio of aluminum oxide to copper powder is 5:1.

[0012] Furthermore, the size of the adsorption column: the diameter is 50 - 60 mm, and the height is 140 - 160 mm.

[0013] Furthermore, 1 CV = 16 mL.

[0014] Furthermore, 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 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 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)propylmethyl phosphate, 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, let stand overnight, filter, wash, and dry to obtain the composite exchange resin.

[0015] Further, in the above A1 reaction process, 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 acts as a surfactant, and sodium hydroxide provides hydroxide ions to form hydroxides in the pores of the activated carbon. Through hydrothermal reaction, the hydroxides decompose when heated 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.

[0016] Further, in 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 be electrostatically combined with the anionic groups in the anion exchange resin, enabling the anion exchange resin to adhere to the surface of the activated carbon loaded with nano-iron oxide to obtain the iron ion adsorption material.

[0017] Further, in 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 be chemically combined with the cationic groups in the cation exchange resin, enabling 3-(trihydroxysilyl)propyl methyl phosphate to be grafted onto the cation exchange resin to complete the phosphorylated cation exchange resin.

[0018] Further, in the above A4 reaction process, oxalic acid acts as a crosslinking agent and can react with the phenolic hydroxyl groups on lignin to form a crosslinked porous structure. And the phosphorylated cation exchange resin and the 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.

[0019] 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.

[0020] Further, in step A2, the mass ratio of the anion exchange resin, deionized water, ethanol, activated carbon loaded with nano iron oxide, and amino silane is (5.6 - 5.8) g : (20 - 30) mL : (75 - 85) mL : (10 - 11) g : (0.5 - 0.9) g.

[0021] Further, in step A3, the dosage ratio of the powdery resin particles, deionized water, ethanol, and 3-(trihydroxysilyl)propyl methyl phosphate is (1.6 - 1.8) g : (8 - 12) mL : (25 - 35) mL : (0.2 - 0.4) g.

[0022] 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.

[0023] Further, the carboxyl content of lignin is 1.6 - 1.66 mmol / g, Hunan Taigelin Paper Group Co., Ltd.

[0024] Further, the amino silane is γ-aminopropyltriethoxysilane.

[0025] The present invention has the following beneficial effects: (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 the 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 amino silane to obtain an iron ion adsorbent. 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 iron elements to be adsorbed into the iron ion adsorbent. On the other hand, the activated carbon loaded with nano iron oxide contained in the iron ion adsorbent provides additional adsorption sites and adsorption capacity, improving the directional extraction of iron isotopes in iron-manganese nodules, increasing the extraction efficiency, reducing the detection error, and the rigid skeleton of the activated carbon inhibits the swelling and deformation of the anion resin in concentrated acid.

[0026] (2) In the technical solution of the present invention, after the cation exchange resin is crushed, ground, and sieved, the aperture of the sieve is 150 meshes to form a porous adsorption resin. And 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 phosphorylated 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.

[0027] (3) In the technical solution of the present invention, the phosphorylated cation exchange resin, iron ion adsorption material, oxalic acid, and lignin are mixed and reacted to form a cross-linked porous structure. And the phosphorylated cation exchange resin and iron ion adsorption material can also be embedded into the porous structure, increasing the cross-linking density and porosity, 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 detection accuracy of metal elements in the iron-manganese nodule. The phosphorylated cation exchange resin and iron ion adsorption material are compounded to form a composite exchange resin and filled into the adsorption column, which can simultaneously extract three isotopes of iron, beryllium, and aluminum in the iron-manganese nodule, reducing the sample demand, reducing the deviation introduced by the analysis of multiple samples, and greatly reducing the experimental time and reagent types, improving work efficiency and economic benefits.

[0028] (4) In the technical solution of the present invention, acid extraction of deep-sea iron-manganese nodules can remove insoluble impurities and interfering substances in the deep-sea iron-manganese nodules, improve the extraction effect of metal elements in the deep-sea iron-manganese nodules, reduce the interference with the analysis results, and improve the accuracy of analysis. In addition, through multiple steps of hydrochloric acid solution and centrifugation, the metal element components in the deep-sea iron-manganese nodules can be further enriched, improving the extraction purity and detectability. Specific embodiments

[0029] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described 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 of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0030] The raw materials used in the embodiments of the present invention are as follows, and all the reagents used are of analytical grade.

[0031] Among them, the activated carbon has a particle size of 3.2 μm and a pore size of 50 nm.

[0032] The carboxyl content of lignin is 1.63 mmol / g, Hunan Taigelin Paper Group Co., Ltd.

[0033] The amino silane is γ-aminopropyltriethoxysilane.

[0034] The anion exchange resin is AG MP-1 anion exchange resin, chloride form, Bio-Rad Laboratories (Shanghai) Co., Ltd.

[0035] The cation exchange resin has the trade name DOWEX50WX8, H form, Shanghai Kayin Chemical Co., Ltd.

[0036] The phosphorylated cation exchange resin: the screen aperture is 150 mesh and the pore size is 0.5 mm.

[0037] The adsorption column size: the diameter is 55 mm, the height is 150 mm, and 1 CV = 16 mL.

[0038] The silver powder model is 7440-22-4, the purity is 99.99%, Thermo Fisher Scientific; the niobium powder model is Nb-003, the purity is 99.99%, Simcere Biochemical Reagents (Shanghai) Co., Ltd.; the copper powder model is CU005140, the purity is 99.99%, GL Biochem (Shanghai) Ltd.

[0039] Example 1 A method for determining the composition of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules, comprising the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; 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; S3. Use 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 part of the iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2; 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 an accelerator mass spectrometer for determination; Among them, in step S1, the specific steps of acid-extracting the deep-sea ferromanganese nodules are: 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; Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to residue a, stir well, soak overnight, and collect the supernatant b and residue b by centrifugation; Place residue b in 20 mL of deionized water, mix evenly, collect the supernatant c by centrifugation. Mix supernatant c, supernatant a, and supernatant b, evaporate to a curd-like state, then add 1 mL of hydrochloric acid with a concentration of 0.05 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; The specific operation of step S2 is as follows: 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; The test sample, 9 Be carrier, 27 The mass ratio of Al carrier is 4.6:0.5:0.5.

[0040] In step S4, the specific operation is as follows: 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 the accelerator mass spectrometer for determination; 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 the accelerator mass spectrometer for determination; 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 the accelerator mass spectrometer for determination; 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 alumina to copper powder is 5:1; The composite ion exchange resin is specifically prepared by the following steps: 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; 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; A3. After the cation exchange resin is crushed, ground and sieved, the mesh aperture of the sieve 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)propylmethyl 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; 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 ion exchange resin.

[0041] Example 2 A method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules, comprising the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with the composite ion exchange resin, oscillate and adsorb for 20-30 min, perform leaching with hydrochloric acid, and collect the iron element leaching solution, beryllium element leaching solution, and aluminum element leaching solution; S3. Use an inductively coupled plasma 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 part of the iron element leaching solution, beryllium element leaching solution, and aluminum element leaching solution taken out in S2; S4. Add ammonia water to the leachate of iron element, beryllium element, and aluminum element 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 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; Among them, in step S1, the specific steps of acid extraction of deep-sea ferromanganese nodules are as follows: 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 centrifuge to collect the supernatant a and the residue a; 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; 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, 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 measure the concentrations of iron element, beryllium element, and aluminum element with an inductively coupled plasma optical / mass spectrometer ICP - AES / MS; The specific operation of step S2 is as follows: 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 leachate of iron element, leach with hydrochloric acid with a concentration of 1 mol / L to 6.5 CV, collect the leachate of beryllium element, and leach with hydrochloric acid with a concentration of 2.5 mol / L to 10.5 CV, collect the leachate of aluminum element; The mass ratio of the test sample, 9 Be carrier, 27 Al carrier is 4.6:0.5:0.5; In step S4, the specific operation is as follows: Mix the leachate of iron element 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 with silver powder, grind them to obtain the target sample, and place the target sample in the target disk of the accelerator mass spectrometer for determination; Mix the leachate of beryllium element 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 with niobium powder, grind them to obtain the target sample, and place the target sample in the target disk of the accelerator mass spectrometer for determination; Mix the aluminum 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; 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.

[0042] The composite ion exchange resin is specifically prepared by the following steps: 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 with deionized water 3 times, and dry in an 80 °C oven for 10 min to obtain activated carbon loaded with nano-iron oxide; 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 with deionized water 3 times, and dry in a 70 °C oven for 10 min to obtain an iron ion adsorbent material; A3. After the cation exchange resin is crushed, ground and sieved, the mesh aperture of the sieve is 130 meshes 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)propyl methyl phosphate, stir and react for 1.5 h, filter, wash with deionized water 3 times, and dry in a 50 °C oven for 10 min to obtain phosphorylated cation exchange resin; A4. Mix 10 g of lignin and 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, stand overnight, filter, wash with deionized water 3 times, and dry in a 50 °C oven for 10 min to obtain the composite ion exchange resin.

[0043] Example 3 A method for determining the composition of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules, comprising the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; S2. The test sample, 9 Be carrier, 27Transfer the Al carrier into an adsorption column filled with composite ion exchange resin, oscillate for adsorption for 20 - 30 min, after leaching with hydrochloric acid, collect the iron element leachate, beryllium element leachate, and aluminum element leachate; 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; 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, obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for determination; Among them, in step S1, the specific steps for acid extraction of deep - sea ferromanganese nodules are as follows: 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 for reaction, soak overnight, and collect the supernatant a and residue a by centrifugation; 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; 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 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; The specific operation of step S2 is as follows: Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with composite ion exchange resin, oscillate for adsorption for 30 min, leach with hydrochloric acid with a concentration of 0.075 mol / L to 2.5 CV, collect the iron element leachate, leach with hydrochloric acid with a concentration of 0.75 mol / L to 6.5 CV, collect the beryllium element leachate, leach with hydrochloric acid with a concentration of 3 mol / L to 10.5 CV, and collect the aluminum element leachate; The test sample, 9 Be carrier, 27 The mass ratio of the Al carrier is 4.6:0.5:0.5.

[0044] In step S4, the specific operation is as follows: 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 the target sample. The target sample is placed in the target disk of an accelerator mass spectrometer for measurement; 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 the target sample. The target sample is placed in the target disk of an accelerator mass spectrometer for measurement; 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 the target sample. The target sample is placed in the target disk of an accelerator mass spectrometer for measurement; 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.

[0045] The composite ion exchange resin is specifically prepared by the following steps: 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; 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; 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; 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 the composite ion exchange resin.

[0046] Comparative Example 1 A method for determining the composition of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules, comprising the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; 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; 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 part of the iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2; 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; Among them, in step S1, the specific steps of acid-extracting the deep-sea ferromanganese nodules are as follows: 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; 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; 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 a 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; The specific operation of step S2 is as follows: 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, leach with 0.1 mol / L hydrochloric acid until 2.5 CV, collect the iron element leachate, leach with 1.0 mol / L hydrochloric acid until 6.5 CV, collect the beryllium element leachate, and leach with 2.5 mol / L hydrochloric acid until 10.5 CV, collect the aluminum element leachate; Test sample, 9 Be carrier, 27 The mass ratio of the Be carrier, the Al carrier is 4.6:0.5:0.5.

[0047] In step S4, the specific operation is as follows: Mix the iron element 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 iron oxide, mix the iron oxide and silver powder, and grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination; Mix the beryllium element 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 beryllium oxide, mix the beryllium oxide and niobium powder, and grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination; Mix the aluminum element 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 aluminum oxide, mix the aluminum oxide 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 determination; 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.

[0048] The composite ion-exchange resin is specifically prepared by the following steps: 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; A2. After the cation exchange resin is crushed, ground, and sieved, the sieve pore size 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)propylmethyl 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; A3. Mix 12 g of lignin with 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 adsorbent material, stir and mix at 60 °C for 20 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 a composite exchange resin.

[0049] Comparative Example 2 A method for determining the composition of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules, comprising the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; S2. Transfer the test sample, 9 Be carrier, 27 Al carrier into an adsorption column filled with a 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; 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; 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; Among them, in step S1, the specific steps for acid-extracting the deep-sea ferromanganese nodules are as follows: 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, centrifuge to collect the supernatant a and the residue a; Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to the residue a, stir evenly, soak overnight, centrifuge to collect the supernatant b and the residue b; 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 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 emission spectrometry / mass spectrometry (ICP-AES / MS) to measure the concentrations of iron element, beryllium element, and aluminum element; The specific operation of step S2 is as follows: Put the test sample, 9 Be carrier, 27 and Al carrier into an adsorption column filled with composite ion-exchange resin, oscillate and adsorb for 30 min, leach with 0.1 mol / L hydrochloric acid until 2.5 CV, collect the iron element leachate, leach with 1.0 mol / L hydrochloric acid until 6.5 CV, collect the beryllium element leachate, and leach with 2.5 mol / L hydrochloric acid until 10.5 CV, collect the aluminum element leachate; The mass ratio of the test sample, 9 Be carrier, 27 and Al carrier is 4.6:0.5:0.5.

[0050] In step S4, the specific operation is as follows: Mix the iron element 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 iron oxide, mix the iron oxide and silver powder, and grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination; Mix the beryllium element 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 beryllium oxide, mix the beryllium oxide and niobium powder, and grind to obtain a target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination; Mix the aluminum element 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 aluminum oxide, mix the aluminum oxide 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 determination; 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.

[0051] The composite ion-exchange resin is specifically prepared by the following steps: 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 80 °C oven for 10 min to obtain activated carbon loaded with nano-iron oxide; 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 a 70 °C oven for 10 min to obtain an iron ion adsorption material; 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)propyl methyl 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; 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, let stand overnight, filter, wash 3 times with deionized water, and dry in an oven at 50 °C for 10 min to obtain composite exchange resin.

[0052] Comparative Example 3 A method for determining the composition of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules, comprising the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; 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, perform leaching with hydrochloric acid, and collect the iron element leachate, beryllium element leachate, and aluminum element leachate; S3. Use an inductively coupled plasma optical 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 part in S2; 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, obtain target samples, and place the target samples in the target disk of an accelerator mass spectrometer for determination; Among them, in step S1, the specific steps for acid-extracting the deep-sea ferromanganese nodules are as follows: Place 5 mg of the 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; 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; 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 curd-like, 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; The specific operation of step S2 is as follows: Transfer the test sample, 9 Be carrier, 27 and the 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; The test sample, 9 Be carrier, 27 and the Al carrier have a mass ratio of 4.6:0.5:0.5.

[0053] In step S4, the specific operation is as follows: 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, and grind to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination; 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, and grind to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination; 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, and grind to obtain the target sample, and place the target sample in the target disk of an accelerator mass spectrometer for determination; 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.

[0054] The composite ion exchange resin is specifically prepared by the following steps: 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; 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; 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; 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 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.

[0055] Comparative Example 4 A method for determining the composition of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules includes the following steps: S1. Acid-extract the deep-sea ferromanganese nodules to obtain a test sample; 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; 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 part of the iron element leachate, beryllium element leachate, and aluminum element leachate taken out in S2; 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; Among them, in step S1, the specific steps for acid-extracting the deep-sea ferromanganese nodules are as follows: 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; Add 10 mL of hydrochloric acid with a concentration of 6 mol / L to residue a, stir well, soak overnight, and collect the supernatant b and residue b by centrifugation; Place residue b in 20 mL of deionized water, mix evenly, collect the supernatant c by centrifugation. Mix supernatant c, supernatant a, and supernatant b, evaporate until it becomes curd-like, 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 using inductively coupled plasma optical / mass spectrometry ICP-AES / MS; The specific operation of step S2 is as follows: 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; The test sample, 9 Be carrier, 27 The mass ratio of Al carrier is 4.6:0.5:0.5.

[0056] In step S4, the specific operation is as follows: 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 the accelerator mass spectrometer for determination; 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 the accelerator mass spectrometer for determination; 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 the accelerator mass spectrometer for determination; 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.

[0057] The composite exchange resin is specifically prepared by the following steps: 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; 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; A3. After the cation exchange resin is crushed, ground and sieved, the mesh aperture of the sieve 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; A4. Mix 4 g of phosphorylated cation exchange resin and 3.6 g of iron ion adsorption material to obtain a composite exchange resin.

[0058] Now, the determination methods of the compositions of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules in Examples 1-3 and Comparative Examples 1-4 are detected.

[0059] 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.

[0060] Use an inductively coupled plasma optical emission spectrometry / mass spectrometry (ICP-AES / MS) to measure the concentrations (mg / L) of the iron element leachate, beryllium element leachate, and aluminum element leachate, which represent the adsorption effect and extraction effect.

[0061] Mix iron oxide and silver powder, beryllium oxide and niobium powder, and aluminum oxide and copper powder, respectively grind them and put them into the target disk of an accelerator mass spectrometer for determination of the ratio, where the 60 Fe / 55 Fe ratio cannot be detected.

[0062] The test results are shown in Tables 1 and 2 below.

[0063] Table 1 Leaching results in Examples 1-3 and Comparative Examples 1-4

[0064] Table 2 Examples 1 - 3 and Comparative Examples 1 - 4 Isotope ratio

[0065] It can be seen from the data in Table 1 and Table 2 that the method for determining the composition of beryllium, aluminum, and iron isotopes in a deep - sea ferromanganese nodule in Examples 1 - 3 has a high recovery rate and a small detection error.

[0066] 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. Its extraction effect decreased and the detection error was large, which proved that nano - iron oxide was synthesized in the pores of the activated carbon, and the hydroxyl groups carried on the surface of the 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.

[0067] 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. Its 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 test sample of the ferromanganese nodule 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.

[0068] In Comparative Example 3, the composite exchange resin prepared by replacing the phosphorylated cation - exchange resin with powdery resin particles was used for the extraction and detection of beryllium, aluminum, and iron isotopes in deep - sea ferromanganese nodules. Its extraction effect decreased and the detection error was large, which proved that 3 - (trihydroxysilyl) propyl methyl 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 test sample of the ferromanganese nodule 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.

[0069] The composite ion exchange resin prepared without adding lignin and oxalic acid in Comparative Example 4 was used for the extraction and detection of beryllium, aluminum, and iron isotopes in deep-sea ferromanganese nodules. Its extraction effect decreased and the detection error was large. It was proved that the phosphorylated cation exchange resin, iron ion adsorption material, oxalic acid, and lignin were mixed and reacted to form a composite ion exchange resin with a cross-linked porous structure and filled into the adsorption column, which could simultaneously extract the three isotopes of iron, beryllium, and aluminum in ferromanganese nodules, reduce the sample demand, and reduce the deviation introduced by the analysis of multiple samples. Moreover, the porous structure had excellent adsorption performance for metal ions, improving the extraction rates of iron, aluminum, and beryllium elements in the test samples of ferromanganese nodules.

[0070] In the description of the specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean 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 representations 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.

[0071] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications, supplements, or use similar methods to replace the specific embodiments described, as long as they do not deviate from the scope defined by the invention, they should fall within the protection scope of the present invention.

Claims

1. A method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules, characterized in that: The following steps are involved: S1. Acid extraction is performed on deep-sea iron-manganese nodules to obtain test samples; the original concentrations of iron, beryllium and aluminum are measured using an ICP-AES / MS plasma optical / mass spectrometer; S2. 9 Be carrier, 27 After the Al carrier is added to the test sample, it is moved into an adsorption column filled with a composite exchange resin, and the adsorption is shaken for 20-30 minutes. After leaching with hydrochloric acid, the iron element leaching solution, the beryllium element leaching solution, and the aluminum element leaching solution are collected; S3. Take the iron, beryllium and aluminum eluents and measure the concentrations of the iron, beryllium and aluminum leaches by ICP-AES / MS to test the recovery rate of the process; S4. Ammonia water is added to the iron element leaching solution, the beryllium element leaching solution, and the aluminum element leaching solution to adjust the pH value to 8-9, and the precipitate is collected by centrifugation, and the precipitate is sintered at 850-950° C. for 1-2 hours to obtain oxides, and the oxides are mixed with silver powder, niobium powder, and copper powder, respectively, and ground to obtain target samples, and the target samples are placed in the target plate of the accelerator mass spectrometer for measurement; The composite exchange resin is obtained by a mixed reaction of a phosphorylated cation exchange resin, an iron adsorption material, oxalic acid and lignin; The iron adsorption material is obtained by mixing activated carbon, ferric chloride hexahydrate and hexadecyltrimethylammonium bromide, and then mixing with aminosilane and anion exchange resin; The phosphorylated cation exchange resin is obtained by crushing, grinding and screening the cation exchange resin and then mixing and reacting it with 3-(trihydroxysilyl)propylmethyl phosphate.

2. The method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that: The composite exchange resin is specifically prepared by the following steps: A1. Add ferric chloride hexahydrate to deionized water, stir evenly, add hexadecyltrimethylammonium bromide, sodium hydroxide and activated carbon, stir and mix at a rate of 500-600r / min for 30-40min, stir and react at 110-130℃ for 10-12h, cool to room temperature, filter, wash and dry to obtain activated carbon loaded with nano-iron oxide; A2. Add anion exchange resin to deionized water and ethanol, stir evenly, add activated carbon loaded with nano-iron oxide and aminosilane, stir and mix at 60-70°C for 2-5h, filter, wash and dry to obtain an iron ion adsorption material; A3. After the cation exchange resin is crushed, ground and sieved, the mesh size is 110-150 mesh to obtain powdered resin particles, the powdered resin particles are added to deionized water and ethanol, stirred evenly, 3-(trihydroxysilyl)propylmethyl phosphate is added, stirred for 1-2h, filtered, washed and dried to obtain a phosphorylated cation exchange resin; A4. Mix lignin and deionized water, stir evenly, add sodium hydroxide aqueous 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 minutes, cool to room temperature, stand overnight, filter, wash and dry to obtain a composite exchange resin.

3. The method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules according to claim 2, characterized in that: In step A1, the ratio of the amount of ferric chloride hexahydrate, deionized water, hexadecyltrimethylammonium 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.

4. The method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules according to claim 2, 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 aminosilane is (5.6-5.8) g: (20-30) mL: (75-85) mL: (10-11) g: (0.5-0.9) g.

5. The method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules according to claim 2, characterized in that: In step A3, the ratio of the powdered resin particles, deionized water, ethanol and 3-(trihydroxysilyl)propylmethyl phosphate is (1.6-1.8) g:(8-12) mL:(25-35) mL:(0.2-0.4) g.

6. The method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules according to claim 2, characterized in that: In step A4, the ratio of the amount of lignin, deionized water, oxalic acid, phosphorylated cation exchange resin and iron ion adsorption material is (8-12) g: (90-120) mL: (1.2-1.4) g: (3-4) g: (3-3.6) g.

7. The method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that: In step S1, the specific steps of acid extraction of deep-sea ferromanganese nodules are as follows: The deep-sea iron-manganese nodule sample was placed in a centrifuge tube, deionized water, hydrochloric acid and hydrogen peroxide were added, and after shaking reaction, it was soaked overnight, and the supernatant a and the residue a were collected by centrifugation; Add hydrochloric acid to the residue a, stir well, soak overnight, and collect the supernatant b and the residue b by centrifugation; The residue b was placed in deionized water and mixed evenly. The supernatant c was collected by centrifugation. The supernatant c, supernatant a and supernatant b were mixed and evaporated to a curd-like state. Hydrochloric acid was then added to dissolve the collected solution. The dissolution was repeated 5 times. The supernatant was collected after centrifugation to obtain a test sample. The test sample was taken to measure the original concentrations of iron, beryllium and aluminum using an ICP-AES / MS plasma optical / mass spectrometer.

8. The method for determining the composition of beryllium, aluminum and iron isotopes in deep-sea ferromanganese nodules according to claim 1, characterized in that: The specific operation of step S2 is: 9 Be carrier, 27 After adding the test sample, the Al carrier is moved into an adsorption column filled with a composite exchange resin, and oscillated and adsorbed for 20-30 minutes. It is leached with 0.05-0.01 mol / L hydrochloric acid to 1-2.5CV, and the iron element leaching liquid is collected. It is leached with 0.5-1.0 mol / L hydrochloric acid to 4.5-6.5CV, and the beryllium element leaching liquid is collected. It is leached with 2-3 mol / L hydrochloric acid to 8.5-10.5CV, and the aluminum element leaching liquid is collected.

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