CN111426764A - Method for testing age of hydrothermal sulfide in quaternary seabed - Google Patents
Method for testing age of hydrothermal sulfide in quaternary seabed Download PDFInfo
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Abstract
The invention provides a test method for the age of a fourth-class submarine hydrothermal sulfide, which is implemented by testing the U/Th isotope ratio of the submarine hydrothermal sulfide by MC-ICPMS230The age calculation method is characterized in that modified strong-base anion exchange resin containing quaternary ammonium salt groups is adopted in U-Th separation and purification, and the modified strong-base anion exchange resin is obtained by reacting chloromethyl styrene-divinylbenzene copolymer microspheres with long-chain tertiary amine and spiro-ring tertiary amine. According to the detection method, the consumption of the annual sample of the multi-metal sulfide on the seabed is smaller, the acid consumption is smaller, the operation is simple, the sample is dissolved more completely, the annual test data is more accurate, and the data reliability and repeatability are better. The technology is simple to operate, and can determine the age and sample amount of uranium thorium of quaternary seafloor sulfideOnly tens of milligrams are needed, and the accuracy of the measured U, Th isotope ratio can be better than 5 per thousand.
Description
Technical Field
The invention belongs to the field of geochemistry, and particularly relates to a method for testing the age of hydrothermal sulfide in the quaternary seabed.
Background
The age of the quaternary seafloor hydrothermal sulfide may provide important information for sulfide deposit formation and modification mechanisms, seafloor hydrothermal activity history, growth rate of large sulfide deposits, and the like. At present, the development and application of MC-ICPMS high-precision mass spectrum technology enable the annual measurement technology to have higher precision and wider annual measurement range, and MC-ICPMS uranium annual measurement is considered as the most reliable quaternary annual measurement means (Cheng et al, 2000,2013; Shen et al, 2008,2013). At present, the uranium dating technology is mainly applied to a quaternary carbonate sample and is less applied to quaternary seabed hydrothermal sulfide, mainly because the carbonate sample is easy to digest and contains less matrix elements, and the sulfide contains a large amount of matrix elements, so that the content of trace element U, Th required by year measurement is lower, and great difficulty is brought to separation work.
It is known that a quaternary undersea sulfide can meet two prerequisites of year measurement of MC-ICPMS uranium system, which are respectively: 1) only U is deposited in the mineral, and no Th is deposited; 2) the post-deposition system remains closed relative to U, Th. The U content of hydrothermal sulfide on the seabed is reported to be about tens of ppb to tens of ppm, and Th is generally less than 1ppm, so that the method is very suitable for a uranium unbalance method for year measurement. The limited place is that seabed polymetallic sulfide belongs to a high matrix sample (containing main elements such as Fe, Zn, Cu, Si, Al, Na and Mg and the like), mineral components are complex, a large amount of metal elements and sulfur elements are contained, the seabed polymetallic sulfide is difficult to digest and is easy to reprecipitate in the experimental process, the recovery rate of Th elements is often too low, the repeatability of experimental results can be poor, the precision and accuracy of the test are affected, and even effective age data cannot be obtained.
The conventional seabed polymetallic sulfide fixed-year sample chemical pretreatment process comprises the following steps: weighing 2-10g sample, using HNO3Or dissolving the sample in aqua regia, dissolving at 85 deg.C for 3 days, and separating insoluble substances. Using Fe3+And NH4OH precipitation of U and Th, Fe (OH)3Matrix removal and U-Th separation after digestion of the precipitate was accomplished by loading onto AG 1-X8 resin the U-Th fraction obtained from the isolation was measured on MC-ICPMS et al instrument and age data were calculated (L alou, C.and Brichet, E., 1987; Kuznetsov et al, 2006; Takamasa et al, 2013; Ishibashi et al, 2015). experiments demonstrated that these procedures were not sufficient to completely dissolve the sample and that the samples were not sufficiently solubleWith the reprecipitation of sulfide and high matrix effect, the accuracy and effectiveness of age data cannot be guaranteed.
On the basis, the development of a quaternary sulfide dating technology which is simple to operate, high in accuracy and strong in repeatability is needed.
Disclosure of Invention
In order to overcome the defect that age accuracy and repeatability are poor in age measurement of quaternary seafloor sulfide uranium thorium by MC-ICPMS in the prior art, the invention designs a set of method for measuring the age of quaternary seafloor sulfide uranium thorium, the problem of incomplete sample dissolution in the year measuring process can be solved by using the method, accuracy and repeatability of U, Th isotope and uranium family year data are improved, the age of quaternary seafloor sulfide is accurately measured, and meanwhile, the application of a uranium family age testing technology in the quaternary sulfide year is expanded.
Specifically, the above object of the present invention is solved by the following technical solutions:
a method for testing the age of hydrothermal sulfide in the quaternary sea bed adopts MC-ICPMS to test the U/Th isotope ratio of hydrothermal sulfide in the sea bed230The age calculation method is characterized in that modified strong-base anion exchange resin is adopted in U-Th separation and purification, and the modified strong-base anion exchange resin is obtained by reacting chloromethyl styrene-divinylbenzene copolymer microspheres with long-chain tertiary amine and spiro-ring tertiary amine.
The mass to volume ratio of the subsea hydrothermal sulfide sample to the modified strongly basic anion exchange resin is 50-60:1(mg/m L).
The quaternary ammonium salt is compounded by long-chain quaternary ammonium salt and spiral quaternary ammonium salt, and the molar ratio of the long-chain quaternary ammonium salt to the spiral quaternary ammonium salt is 5-8: 1.
the long-chain tertiary amine is a tertiary amine containing a carbon chain of 8 to 20 carbon atoms, such as fatty alkyldimethylamine, fatty alkyldiethylamine, the fatty alkyl group being selected from alkyl groups of 8 to 20 carbon atoms, such as octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl; the spiro cyclic tertiary amine is a spiro ring containing nitrogen atoms, and the spiro ring contains 8-16 carbon atoms and 1-3 nitrogen atoms; specifically, the spiro cyclic tertiary amine is selected from N-methyl-3-azaspiro [5,5] undecane, 2, 8-diaza-spiro [4,5] decane, 1,3, 8-triaza-spiro [4.5] decane, 4, 8-diaza-spiro [4,5] decane, 8-aza-spiro [4,5] decane.
The modified strong-base anion exchange resin is prepared by a preparation method comprising the following steps: swelling chloromethyl styrene-divinylbenzene copolymer microspheres with a solvent, adding mixed amine of long-chain tertiary amine and spiro tertiary amine under stirring, heating, washing after the reaction is finished, and drying to obtain the strong-base anion exchange resin.
The preparation of the chloromethylstyrene-divinylbenzene copolymer microspheres is well known in the art, and is not particularly limited, and the degree of crosslinking is generally controlled to be 8 to 15%.
The solvent used for the microspheres of chloromethylstyrene-divinylbenzene copolymer is not particularly limited, and examples thereof include toluene, nitrobenzene, ethanol, dichloromethane, chloroform, and the like. The mass ratio of the solvent to the microspheres is 3-5:1, the swelling time is not particularly limited, and the microspheres can be fully swelled, generally 12-24 hours.
Further, the mole ratio of the long-chain tertiary amine to the spiro tertiary amine is 5-8: 1, the mass ratio of the chloromethyl styrene-divinylbenzene copolymer microspheres to the mixed amine is 1:1-2, preferably 1: 1.5-1.7. The feeding mode of the mixed amine can be directly feeding, and can also be configured to be feeding of a solution with the mass fraction of 30-50%, and the solvent of the solution can be water, methanol, ethanol, acetonitrile, ethyl acetate and the like.
The heating is carried out until the temperature is 40-70 ℃, and the reaction lasts 24-48 hours.
The inventor unexpectedly finds that the obtained resin has very good separation effect on uranium and thorium in a sample by synthesizing a novel strong-base anion exchange resin with long-chain quaternary ammonium salt and cyclic quaternary ammonium salt, and can successfully complete the separation of trace uranium and thorium in a geological sample by adopting specific elution separation conditions.
Preferably, the above-mentioned quaternary seafloor hydrothermal sulfide age test method of the present invention comprises the following steps:
(1) digesting a sample; taking a proper amount of sample, putting the sample into a sample dissolving tank, adding acid for repeated dissolution, evaporating to dryness, and adding229Th-233U-236U diluent, evaporating the sample;
(2) U-Th separation: dissolving the evaporated sample by acid, loading the sample on modified strong-base anion exchange resin for U-Th separation, eluting matrix elements, respectively collecting Th isotope components and U isotope components, respectively evaporating, dissolving the evaporated sample, and performing mass spectrometry;
(3) mass spectrometry: collected U, Th isotopes are tested by MC-ICPMS, and isotope fractionation correction, mass correction and chronological calculation are completed on data collected by the instrument.
Further preferably, a quaternary seafloor hydrothermal sulfide age test method comprises the following steps:
(1) sample treatment: putting 20-30mg of sample into a sample dissolving tank, adding hydrochloric acid 1, hydrofluoric acid and perchloric acid, carrying out first constant temperature heating, cooling, then adding nitric acid 1, carrying out second constant temperature heating, cooling, then evaporating to dryness, adding hydrochloric acid 2 to dissolve the sample, adding hydrochloric acid 2 into the sample229Th-233U-236U diluent, evaporating the sample;
(2) U-Th separation: loading a sample which is completely dissolved and evaporated by nitric acid 2 to a modified strong-base ion exchange resin column, adding nitric acid 3 to the resin to elute a matrix element, adding hydrochloric acid 3 to the resin, collecting Th isotope components, adding nitric acid 4 to the resin, collecting U isotope components, collecting, evaporating, re-dissolving by nitric acid 5, evaporating again, dissolving the evaporated sample by using nitric acid/hydrofluoric acid mixed acid, and measuring by mass spectrum;
(3) mass spectrometry: the collected U, Th isotope is tested by MC-ICPMS, and the data collected by the instrument is subjected to isotope fractionation correction, quality correction and chronological calculation.
The sample is a quaternary seabed sulfide sample collected in the field, after surface dirt is removed by a physical means, a fresh and compact part is selected and a trace sample is taken in a ventilation cabinet, and cross contamination is avoided to the maximum extent in the sampling process.
Preferably, the concentration of hydrochloric acid 1 is 10-12M, the dosage is 1-2M L, the dosage of hydrofluoric acid is 40-50 wt% hydrofluoric acid, the dosage is 0.5-1M L, the concentration of perchloric acid is 50-70 wt%, the dosage is 0.1-0.2M L, the concentration of nitric acid 1 is 10-14M, the dosage is 0.5-1M L, the concentration of hydrochloric acid 2 is 10-12M, the dosage is 0.5-1M L, the concentration of nitric acid 2 is 7-10M, the dosage is 0.1-0.5M L, the concentration of nitric acid 3 is 7-10M, the dosage is 2-3M L, the concentration of hydrochloric acid 3 is 8-12M, the dosage is 1-3M L, the concentration of nitric acid 4 is 0.01-0.1M, the dosage is 2-3M L, the concentration of nitric acid 5 is 10-14M, the dosage is 2-5M, the concentration of nitric acid/hydrofluoric acid is 2-4 wt%, the concentration of hydrofluoric acid is 0.05-0.05 wt%, and the dosage is 0.05-2M L M.
In the sample treatment in the step (1), the first constant temperature heating refers to heating to 120-130 ℃, and keeping the constant temperature for 12-15 h; the second constant temperature heating is to heat to 110 ℃ at 100-.
In the step (2) of U-Th separation, adding229Th-233U-236After U diluent, in the system235U/233The ratio of U is 10-20,229Th/230the ratio of Th is less than 1000, said229Th/230The ratio of Th less than 1000 means229Th/230Th is 0.001 to 1000, preferably 0.02 to 50.
The MC-ICPMS in the step (3) is measured by adopting an SEM/Faraday mixing cup structure, and preferably, the mixing cup structure is shown in the following table 1:
TABLE 1
Note that L1-L3, H1-H3 represent receiver types, C represents the center cup position, where SEM represents a secondary electron multiplier for receiving current signals <10mV, and Faraday represents a Faraday cup receiver for receiving current signals between 10mV and 50V.
Compared with the prior art, the invention has the following advantages:
according to the detection method, the annual sample consumption of the seabed polymetallic sulfide is smaller, the acid consumption is smaller, the operation is simple, the sample is dissolved more completely, the annual test data is more accurate, and the data reliability and repeatability are better. The technology is simple to operate, the age of uranium thorium of the quaternary seafloor sulfide can be determined, the sample amount is only dozens of milligrams, and the accuracy of the measured U, Th isotope ratio can be superior to 5 per thousand.
The MC-ICPMS uranium dating technology is adopted to test the age of the fourth submarine hydrothermal sulfide, and the strong-base anion exchange resin containing the long-chain quaternary ammonium salt and the spiro-ring quaternary ammonium salt is adopted, so that the consumption of a tested sample can be reduced by one to two orders of magnitude, the mixed dyeing of multiple samples caused by large sample consumption is greatly reduced, and the detection accuracy is ensured.
Thirdly, aiming at the hydrothermal fluid sulfide sample at the quaternary seabed, the dosage and the concentration of eluent used for separating and purifying U, Th elements are optimized, and a specific mixing cup structure is optimized, so that the sulfur sample is prepared230Th/232The Th ratio test is more accurate, the sample consumption is less, and the technical guarantee is laid for obtaining the absolute age data of the hydrothermal sulfide sample in the quaternary seabed.
Drawings
FIG. 1 is a schematic of a sample processing and detection scheme of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The experimental methods in the following examples, which are not specifically described, were all carried out in an ultraclean chemical laboratory, and the various reagents used were of ultra-pure grade, or were purified by multiple distillations, and were commercially available; the instruments used were all of the Neptune Plus model MC-ICPMS manufactured by Thermo Fisher, USA; the samples were all homogeneous powder samples of the same sample, taken from the western Indian ocean ridge.
Preparation example 1
Swelling 10g of chloromethyl styrene-divinylbenzene copolymer microspheres with the crosslinking degree of 8% by 40g of absolute ethyl alcohol, adding 15g of dodecyl dimethyl amine and 40 wt% of methanol solution of mixed amine of 2, 8-diaza-spiro [4,5] decane under stirring, wherein the molar ratio of the dodecyl dimethyl amine to the 2, 8-diaza-spiro [4,5] decane is 5:1, slowly stirring, heating to 45 ℃ for reaction for 48 hours, leaching with 5 wt% of NaOH after the reaction is finished, leaching to neutrality by using a large amount of deionized water, and vacuum drying to obtain the strongly basic anion exchange resin, hereinafter referred to as anion exchange resin 1.
Preparation example 2
The preparation method and conditions were the same as in preparation example 1 except that dodecyldimethylamine and 2, 8-diaza-spiro [4,5] decane were added in a molar ratio of 8:1 in the mixed amine solution. Finally preparing the anion exchange resin 2.
Preparation example 3
The preparation method and conditions were the same as in preparation example 1 except that dodecyldimethylamine and 2, 8-diaza-spiro [4,5] decane were added in a molar ratio of 3:1 in the mixed amine solution. Finally preparing the anion exchange resin 3.
Preparation example 4
The preparation method and conditions were the same as in preparation example 1 except that the molar ratio of dodecyldimethylamine to 2, 8-diaza-spiro [4,5] decane was 10:1 in the mixed amine solution added. Finally preparing the anion exchange resin 4.
Comparative preparation example 1
The preparation method and conditions were the same as in preparation example 1, except that the amine solution added was 30g of dodecyldimethylamine in 40 wt% methanol, i.e., no 2, 8-diaza-spiro [4,5] decane was added. Finally, the anion exchange resin 5 is prepared.
Comparative preparation example 2
The preparation and conditions were the same as in preparation example 1, except that the amine solution added was a 40 wt% methanol solution of 30g of 2, 8-diaza-spiro [4,5] decane, i.e., no dodecyldimethylamine was added. Finally preparing the anion exchange resin 6.
Example 1
(1) Selecting a sample: a hydrothermal sulfide sample collected from the ocean floor of the southwest Indian ocean is selected, dirt on the surface of the sample is cut off, a fresh surface is leaked out, a middle fresh compact part is selected to be collected in a ventilation cabinet by a nicking tool, and the cross contamination is avoided.
(2) Sample dissolution 30mg of the sample was weighed into a 7ml PFA sample dissolution tank with a lid, and 1.5M of hydrochloric acid of 12M concentration L, 0.5ml of 40 wt% hydrofluoric acid and 0.1ml of 65 wt% HClO were added4Sealing the sample dissolving tank, heating to 120 deg.C on low temperature electric heating plate, heating at constant temperature for 12 hr, cooling to room temperature, opening the sample dissolving tank, and adding 0.5ml HNO with concentration of 14M into the sample solution3And if bubbles appear, reducing the amount of the bubbles after 15min, closing the sample dissolving tank, putting the sample dissolving tank on an electric hot plate, heating to 110 ℃, heating for 4h at constant temperature, opening the sample dissolving tank after cooling, and evaporating the sample on the electric hot plate. 0.5ml of 12M hydrochloric acid was added to the sample, and 0.1g of the total solution was added to the sample229Th-233U-236U diluent (in mixed liquor)235U/233U≈15，229Th/230Th is about 200), placing on a hot plate, and drying at 150 deg.C.
(3) U-Th separation: the sample was dried by using 0.2ml of 7M dilute nitric acid, and loaded on 0.5ml of a clean anion exchange resin column 1 prepared in preparation example 1, and 3ml of 7M HNO was added to the resin3Eluting a large amount of matrix elements such as Fe and Cu, adding 1ml of 12M HCl to the resin, collecting Th isotope components using a clean 7ml PFA sample dissolving tank, adding 2ml of 0.01M nitric acid to the resin, and collecting U isotope components using a clean 7ml PFA sample dissolving tank. Collecting, drying at 150 deg.C on a constant temperature electric heating plate, and dripping 2 drops of 14M HNO3Redissolving, steaming to near dryness, and adding 0.3m L2 wt% HNO30.1 wt% HF dissolves the evaporated sample to be measured by mass spectrometry.
(4) Mass spectrometry: collected U, Th isotopes are tested by using MC-ICPMS, and data collected by the instrument are subjected to isotope fractionation correction, mass correction, chronological calculation and the like in Excel. The signals and stability of the instrument were monitored before and after the sample measurement using U standard solution NBS-CRM 112A with a given isotope ratio, and the specific instrument parameters and cup structures used for data acquisition are shown in tables 2 and 3.
TABLE 2
(5) The data obtained were calculated using Excel, and the formula is shown below:
the results of the data obtained are shown in Table 4.
And (3) evaluating data: for samples in open-ended oceans, of samples234U and234UinitialThe values being generally in ocean waters234Around the mean value of U (144.9. + -. 0.1% o, Andersen et al, 2010), this time for the sulfide Y sample234U and234Uinitial146 + -2% and 147 + -2% respectively, the U content is 4.8ppm, slightly higher than the average value of seawater (about 3ppm), which indicates the data are reasonable; uncorrected230The Th age is 738 + -5 years, and the age precision is 6.8 per mill. These show that the method can accurately determine the uranium-based age of the seafloor sulfide.
Example 2
Other operations and conditions were the same as in example 1 except that the anion exchange resin 1 in the separation and purification of U-Th in step (3) was replaced with the anion exchange resin 2, and the test results are shown in Table 4.
Example 3
Other operations and conditions were the same as in example 1 except that the anion exchange resin 1 in the separation and purification of U-Th in step (3) was replaced with the anion exchange resin 3, and the test results are shown in Table 4.
Example 4
Other operations and conditions were the same as in example 1 except that the anion exchange resin 1 in the separation and purification of U-Th in step (3) was replaced with the anion exchange resin 4, and the test results are shown in Table 4.
Comparative example 1
Other operations and conditions were the same as in example 1 except that the anion exchange resin 1 in the separation and purification of U to Th in step (3) was replaced with AG 1-X8 anion exchange resin, and the test results are shown in Table 4.
Comparative example 2
The other operations and conditions were the same as in example 1 except that the anion exchange resin 1 in the separation and purification of U to Th in step (3) was replaced with the anion exchange resin 5, and the test results are shown in Table 4.
Comparative example 3
Other operations and conditions were the same as in example 1 except that the anion exchange resin 1 in the separation and purification of U to Th in step (3) was replaced with the anion exchange resin 6, and the test results are shown in Table 4.
TABLE 4 of subsea sulfide Y samples230Th dating results (+/-2 sigma)
TABLE 4
2 σ represents 2 times the standard deviation.
*234U＝([234U/238U]Activity of the invention–1)×1000。
**234UInitialAccording to230Calculation of Th age (T), e.g.234UInitial＝234UTesting×eλ234×TAnd λ represents a decay constant.230Th corrected age according to initial230Th/232Th atomic ratio 4.4 + -2.2 x10-6Calculated as the ratio ofThe ratio of long-term balance substances is equal to that of solid earth232Th/238The U ratio is 3.8, and the error is assumed to be 50%.
B.p. means "Before Present" defined as 2000 A.D.
As can be seen from the data in Table 4, the U/Th separation is carried out by adopting the modified strong-base anion exchange resin containing the long-chain alkyl quaternary ammonium salt and the spiral ring-shaped quaternary ammonium salt according to the method of the invention, so that the U, Th element content of the sulfide sample is tested with higher precision,230Th/232Th、234U/238u and230Th/238the error of the U ratio test is smaller, and the error of the age is also smaller; the sample dosage is smaller, the mixed dyeing of multi-phase samples caused by large sample dosage is avoided to the greatest extent, and the uranium age data accuracy, reliability and repeatability of the hydrothermal sulfide sample at the quaternary sea bottom are better.
Claims (10)
1. A method for testing the age of hydrothermal sulfide in the quaternary sea bed adopts MC-ICPMS to test the U/Th isotope ratio of hydrothermal sulfide in the sea bed230The age calculation method is characterized in that modified strong-base anion exchange resin containing quaternary ammonium salt groups is adopted in U-Th separation and purification, and the modified strong-base anion exchange resin is obtained by reacting chloromethyl styrene-divinylbenzene copolymer microspheres with long-chain tertiary amine and spiro-ring tertiary amine.
2. The test method of claim 1, wherein the mass to volume ratio of the subsea hydrothermal sulfide sample and the modified strongly basic anion exchange resin is 50-60:1(mg/m L).
3. The test method according to claim 1, wherein the molar ratio of the long-chain tertiary amine to the spiro tertiary amine is 5 to 8: 1.
4. the test method according to claim 1, characterized in that the long-chain tertiary amine is a tertiary amine containing a carbon chain of 8 to 20 carbon atoms, such as fatty alkyldimethylamine, fatty alkyldiethylamine, the fatty alkyl being chosen from alkyl groups of 8 to 20 carbon atoms, such as octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl; the spiro cyclic tertiary amine is a spiro ring containing nitrogen atoms, and the spiro ring contains 8-16 carbon atoms and 1-3 nitrogen atoms; specifically, the spiro cyclic tertiary amine is selected from N-methyl-3-azaspiro [5,5] undecane, 2, 8-diaza-spiro [4,5] decane, 1,3, 8-triaza-spiro [4.5] decane, 4, 8-diaza-spiro [4,5] decane, 8-aza-spiro [4,5] decane.
5. The test method of claim 1, wherein the modified strongly basic anion exchange resin is prepared by a preparation method comprising the steps of: swelling chloromethylstyrene-divinylbenzene copolymer microspheres with a solvent, adding mixed amine of long-chain tertiary amine and spiro-ring tertiary amine under stirring, heating, washing and drying after reaction is finished to obtain the strong-base anion exchange resin, wherein the mass ratio of the chloromethylstyrene-divinylbenzene copolymer microspheres to the mixed amine is preferably 1:1-2, and preferably 1: 1.5-1.7.
6. The test method according to any one of claims 1 to 5, comprising the steps of:
(1) digesting a sample; taking a proper amount of sample, putting the sample into a sample dissolving tank, adding acid for repeated dissolution, evaporating to dryness, and adding229Th-233U-236U diluent, evaporating the sample;
(2) U-Th separation: dissolving the evaporated sample by acid, loading the sample on modified strong-base anion exchange resin for U-Th separation, eluting matrix elements, respectively collecting Th isotope components and U isotope components, respectively evaporating, dissolving the evaporated sample, and performing mass spectrometry;
(3) mass spectrometry: collected U, Th isotopes are tested by MC-ICPMS, and isotope fractionation correction, mass correction and chronological calculation are completed on data collected by the instrument.
7. The test method of claim 6, comprising the steps of:
(1) sample treatment: putting 20-30mg of sample into a sample dissolving tank, adding hydrochloric acid 1, hydrofluoric acid and perchloric acid, carrying out first constant temperature heating, cooling, then adding nitric acid 1, carrying out second constant temperature heating, cooling, then evaporating to dryness, adding hydrochloric acid 2 to dissolve the sample, adding hydrochloric acid 2 into the sample229Th-233U-236U diluent, evaporating the sample;
(2) U-Th separation: loading a sample which is completely dissolved and evaporated by nitric acid 2 to a modified strong-base ion exchange resin column, adding nitric acid 3 to the resin to elute a matrix element, adding hydrochloric acid 3 to the resin, collecting Th isotope components, adding nitric acid 4 to the resin, collecting U isotope components, collecting, evaporating, re-dissolving by nitric acid 5, evaporating again, dissolving the evaporated sample by using nitric acid/hydrofluoric acid mixed acid, and measuring by mass spectrum;
(3) mass spectrometry: the collected U, Th isotope is tested by MC-ICPMS, and the data collected by the instrument is subjected to isotope fractionation correction, quality correction and chronological calculation.
8. The test method according to claim 7, wherein the hydrochloric acid 1 has a concentration of 10 to 12M in an amount of 1 to 2M L, the hydrofluoric acid has a concentration of 40 to 50 wt% hydrofluoric acid in an amount of 0.5 to 1M L, the perchloric acid has a concentration of 50 to 70 wt% in an amount of 0.1 to 0.2M L, the nitric acid 1 has a concentration of 10 to 14M in an amount of 0.5 to 1M L, the hydrochloric acid 2 has a concentration of 10 to 12M in an amount of 0.5 to 1M L, the nitric acid 2 has a concentration of 7 to 10M in an amount of 0.1 to 0.5M L, the nitric acid 3 has a concentration of 7 to 10M in an amount of 2 to 3M L, the hydrochloric acid 3M in an amount of 8 to 12M in an amount of 2 to 3M L, the nitric acid 4 has a concentration of 0.01 to 0.1M in an amount of 2 to 3M L, the nitric acid 5 has a concentration of 10 to 14M, the hydrofluoric acid has a concentration of 2 to 5 drops/hydrofluoric acid of 0.05 wt% in an amount of 0.1 to 1M L wt%.
9. The test method of claim 6 or 7, wherein the test method is characterized by229Th-233U-236The addition amount of the U diluent meets the requirement of the mixed solution229Th/230The ratio of Th is less than 1000, said229Th/230The ratio of Th less than 1000 means229Th/230Th is 0.001 to 1000, preferably 0.02 to 50.
10. The test method according to claim 6 or 7, wherein the MC-ICPMS in step (3) is determined using a SEM/Faraday hybrid cup structure, preferably the hybrid cup structure is as follows:
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| CN115993391A (en) * | 2023-03-22 | 2023-04-21 | 中国科学院地质与地球物理研究所 | Method for determining years and analyzing Mg isotopes of fourth-period rock salt sample U-Th |
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