CN114184667A - Method and system for analyzing neodymium isotope in rare earth-rich neodymium element mineral - Google Patents
Method and system for analyzing neodymium isotope in rare earth-rich neodymium element mineral Download PDFInfo
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- 229910052779 Neodymium Inorganic materials 0.000 title claims abstract description 90
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 41
- 239000011707 mineral Substances 0.000 title claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 26
- 238000005194 fractionation Methods 0.000 claims abstract description 31
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- 238000004364 calculation method Methods 0.000 claims abstract description 17
- 238000012360 testing method Methods 0.000 claims abstract description 17
- 238000000608 laser ablation Methods 0.000 claims abstract description 16
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- 239000011435 rock Substances 0.000 claims abstract description 12
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- 238000005259 measurement Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 2
- 238000000176 thermal ionisation mass spectrometry Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010438 granite Substances 0.000 description 2
- 229910052590 monazite Inorganic materials 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 102000014150 Interferons Human genes 0.000 description 1
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- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229940079322 interferon Drugs 0.000 description 1
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Abstract
The invention belongs to the technical field of all-rock neodymium isotope testing, and discloses a method and a system for analyzing neodymium isotopes in rare earth-rich neodymium element minerals, wherein an instrument which is combined by a laser ablation system and an inductively coupled plasma mass spectrometer is used for collecting signals with the mass numbers of 142,143,144,145,146,147 and 149 in a standard sample and an unknown sample; of Sm in the sample144Sm isotope pair144Interference of Nd147And subtracting the Sm signal and the isotope natural abundance of the element Sm, and correcting the element fractionation effect and the mass discrimination effect by adopting an external standard method. The invention shortens the debugging time of the instrument, improves the experimental efficiency, and compiles data processing software 'Nada' for batch calculation, abnormal screening, peak filtering and data result formatting; and performing neodymium isotope tests in sequence, wherein the result is consistent with the recommended value within the error range.
Description
Technical Field
The invention belongs to the technical field of all-rock neodymium isotope testing, and particularly relates to a method and a system for analyzing neodymium isotopes in rare earth-rich neodymium element minerals.
Background
Neodymium (Nd) is a rare earth element, belonging to key and strategic metal minerals, and plays an important role in the rare earth field and controls the rare earth market. The content of neodymium element in the earth crust is 38ppm, and the neodymium element is widely present in various rocks and minerals in the nature. Neodymium has 7 isotopes: 142Nd, 143Nd, 144Nd, 145Nd, 146Nd, 148Nd, and 150Nd, respectively, with their relative abundances: 27.09%, 12.14%, 23.83%, 8.29%, 17.26%, 5.74%, and 5.63%, wherein 143Nd is a daughter isotope formed from 147Sm by alpha decay. A plurality of neodymium isotope reservoirs exist in an earth system, through a long geological history, the neodymium isotope composition characteristics of different end members are different due to long-time geological evolution, the geological source of a sample can be traced by testing the neodymium isotope composition in the sample, and further the evolution history of a shell mantle is revealed.
The neodymium isotope analysis can be carried out on the rock by adopting the thermal ionization mass spectrum or the multi-receiving plasma mass spectrometer, however, when the neodymium isotope analysis is applied to metamorphic rocks and ore samples, the multi-resolution is often presented, and the whole-rock isotope result is incapable of being used in the evolution and mineralization process of finely-drawn magma, so that more and more researchers in recent years begin to explore the in-situ micro-area neodymium isotope analysis technology of the ore by adopting an instrument which is combined by a laser ablation system and the multi-receiving plasma mass spectrometer. The neodymium isotope analysis inevitably faces to the element fractionation effect and the isotope quality discrimination effect of the instrument, and needs a practical and effective test method to correct the isotope quality discrimination effect, the existing method adopts an internal standard method, namely adopts 146Nd/144Nd (0.7219) -0.7219 to carry out index normalization to correct the isotope quality discrimination effect of the instrument, and does not consider the element fractionation effect generated in the laser ablation process, so that each test needs a lot of time to optimize laser and mass spectrum parameters, and is time-consuming and labor-consuming.
In addition, there is no practical and effective automatic data processing program, and it takes about 10 minutes to manually calculate one data, while tens of Nd isotope test data are often obtained by one sample, and the calculation work of a large sample amount is a very time-consuming and labor-consuming process.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) the existing internal standard method can not solve the element fractionation effect, and can obtain an acceptable correction result only by repeatedly optimizing laser and mass spectrum parameters within a large amount of time.
(2) The calculation work related to the research of the neodymium isotope is completed through manual calculation, the calculation work is heavy, and a mature and highly automated neodymium-rich mineral neodymium isotope analysis data processing program is lacked.
The difficulty in solving the above problems and defects is:
(1) the element fractionation effect is neglected, and the neodymium isotope is difficult to be measured, because the Sm element does not have a pair of interference-free isotope pairs for calculating the fractionation factor, the traditional internal standard method has no function of fractionating the Sm element, so that accurate 144Sm cannot be obtained to deduct the interference of the Sm on 144Nd, and a sufficiently accurate Nd isotope result cannot be measured. The traditional method reduces the element fractionation effect by repeatedly debugging the instrument parameters, and is time-consuming, labor-consuming and financial-consuming.
(2) The difficulty in compiling a mature and highly automated neodymium-rich mineral neodymium isotope analysis data processing program is to master computer languages and isotope calculation theories at the same time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method and a system for analyzing neodymium isotopes in rare earth-rich neodymium minerals.
The invention is realized in this way, the method for analyzing the neodymium isotope in the rare earth-rich neodymium mineral adopts an instrument which combines a laser ablation system and an inductively coupled plasma mass spectrometer to collect signals with the mass numbers of 142,143,144,145,146,147 and 149 in a standard sample and an unknown sample; of Sm in the sample144Sm isotope pair144Interference of Nd147SmThe signal of (2) and the isotope natural abundance of the element Sm are deducted, and an external standard method is adopted to correct the element fractionation effect and the mass discrimination effect.
Further, the homogeneous allotropic element interference deduction calculation formula of the analysis method of the neodymium isotope in the rare earth-rich neodymium element mineral is as follows:
144Smt=144Smm-[147Smm×(144SmM/147SmM)];
wherein t represents the true value, M represents the measured value, and M represents the natural abundance of the isotope.
Further, the correction calculation of isotope fractionation in the test process of the analysis method of the neodymium isotope in the rare earth-rich neodymium element mineral follows an exponential fractionation law, and the formula is as follows:
β=ln(Rm/Rt)/ln(MA/MB);
wherein β is a mass discrimination correction coefficient, Rm is an actual measurement ratio, Rt is a true ratio, MA is an accurate mass number of the isotope a, and MB is an accurate mass number of the isotope B. Isotopic fractionation of Sm using beta147Sm/149Sm is corrected, and isotope fractionation of Nd element adopts beta146Nd/144Nd is corrected.
Furthermore, the method for analyzing the neodymium isotope in the rare earth-rich neodymium element mineral adopts an external standard method to correct the element fractionation effect and the quality discrimination effect of the instrument on the isotope, namely the real value and the measured value of the standard sample are calculated to obtain the isotope quality discrimination effect146Nd/144Substituting the actual ratio of Nd into a formula to calculate a correction factor, and further correcting and calculating an element fractionation effect in the laser ablation process and a quality discrimination effect generated in the test process; to obtain finally143Ndt/144NdtThe geological source of the sample is traced, and the evolution history of the shell mantle is further revealed.
It is a further object of the invention to provide a computer device comprising a memory and a processor, the memory storing a computer program which, when executed by the processor, causes the processor to perform the steps of the method of analyzing a neodymium isotope in a rare earth-rich neodymium element mineral.
Another object of the present invention is to provide a computer-readable storage medium storing a computer program which, when executed by a processor, causes the processor to perform the steps of the method for analyzing a neodymium isotope in a rare earth-rich neodymium element mineral.
Another object of the present invention is to provide an information data processing terminal, which is used for implementing the method for analyzing the neodymium isotope in the rare earth-rich neodymium mineral.
Another object of the present invention is to provide a tracing system for geological origin of neodymium isotope in a neodymium-rich mineral, which implements the method for analyzing neodymium isotope in a rare earth-neodymium-rich mineral, the tracing system for geological origin of neodymium isotope in a neodymium-rich mineral including:
the Nd Calibration module is used for element fractionation, quality discrimination and interference correction calculation and has the functions of screening and prompting abnormal data;
the data Filter module is used for automatically processing abnormal data, filtering the abnormal data of the abnormal signal of each laser ablation point, deleting the data with the difference of more than 2.5 times of standard error from the signal mean value according to the filtering principle, acquiring 200 signal data for each laser ablation point, prompting a user to manually check the data when the deletion amount is more than or equal to one third, and analyzing the specific reason of the abnormality;
nd result table module for calculating beta147Sm/149Sm、β146Nd/144Nd、147Sm/144Nd n、143Nd/144Nd n、145Nd/144The value of Nd n, n being normalized, and the normalized value, and formatting the result.
By combining all the technical schemes, the invention has the advantages and positive effects that:
(1) the traditional mineral Nd isotope testing method needs to repeatedly debug instruments to overcome the influence of element fractionation and quality discrimination effect, and has low efficiency and low precision. The technical method of the invention overcomes the technical prejudice;
(2) the invention greatly improves the precision of the mineral neodymium isotope, greatly shortens the debugging time of the instrument and improves the experimental efficiency; the invention adopts Visual Basic language to compile a highly intelligent automatic calculation program 'Sara', saves the heavy work of manual calculation in geological work, improves the work efficiency by more than one hundred times, and can provide better service for geological and geological isotope work.
Drawings
Fig. 1 is a flowchart of a method for analyzing a neodymium isotope in a rare earth-rich neodymium mineral according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of the structure of a tracing system of geological origin of neodymium-rich mineral neodymium isotope provided by the embodiment of the invention;
in fig. 2: 1. an Nd Calibration module; 2. a DataFilter module; 3. nd result table module.
FIGS. 3(a) and 3(b) are results of isotope production of Nd, which is an apatite standard substance according to an example of the present invention.
Fig. 4(a) and 4(b) show the results of the isotope of the sphene standard substance Nd according to the example of the present invention.
Fig. 5(a), 5(b) and 5(c) are the results of Nd isotope in monazite samples provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a method and a system for analyzing neodymium isotopes in rare earth-rich neodymium minerals, and the invention is described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the method for analyzing neodymium isotopes in rare earth-rich neodymium mineral provided by the invention comprises the following steps:
s101: collecting signals with the mass numbers of 142,143,144,145,146,147 and 149 in a standard sample and an unknown sample by using an instrument which is used for combining a laser ablation system and an inductively coupled plasma mass spectrometer;
s102: of Sm in the sample144Sm isotope pair144Interference of Nd147Deducting the signal of Sm and the natural abundance of the isotope of element Sm;
s103: and correcting the element fractionation effect and the quality discrimination effect by adopting an external standard method.
As shown in fig. 2, the tracing system for geological source of neodymium isotope of neodymium-rich mineral provided by the invention comprises:
and the Nd Calibration module 1 is used for element fractionation, quality discrimination and interference correction calculation, and is provided with functions of screening and prompting abnormal data.
The DataFilter module 2 is used for automatically processing abnormal data, filtering the abnormal data of the abnormal signal of each laser ablation point, deleting the data with the difference of more than 2.5 times of standard error from the signal mean value according to the filtering principle, acquiring 200 signal data of each laser ablation point, and prompting a user to manually check the data when the deletion amount is more than or equal to one third, and analyzing the specific reason of the abnormality.
Nd result table module 3 for calculating beta147Sm/149Sm、β146Nd/144Nd、147Sm/144Nd n、143Nd/144Nd n、145Nd/144Nd n values (n means normalized, and normalized values), and the results are formatted.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1:
the invention adopts an instrument which is combined by a laser ablation system and an inductively coupled plasma mass spectrometer to collect signals with the mass numbers of 142,143,144,145,146,147 and 149 in a standard sample and an unknown sample, and Sm in the samples144Sm isotope pair144Interference of Nd147And subtracting the signal of Sm and the isotope natural abundance of element Sm.
The isobaric interferon deduction calculation formula is as follows:
144Smt=144Smm-[147Smm×(144SmM/147SmM)];
wherein t represents the true value, M represents the measured value, and M represents the natural abundance of the isotope.
The correction calculation of isotope fractionation in the test process of the invention follows the law of exponential fractionation, with the following formula:
β=ln(Rm/Rt)/ln(MA/MB);
wherein β is a mass discrimination correction coefficient, Rm is an actual measurement ratio, Rt is a true ratio, MA is an accurate mass number of the isotope a, and MB is an accurate mass number of the isotope B. Isotopic fractionation of Sm using beta147Sm/149Sm is corrected, and isotope fractionation of Nd element adopts beta146Nd/144Nd is corrected.
The past method adopts146Nd/144Carrying out index normalization on Nd-0.7219 to obtain a correction factor beta146Nd/144Nd, the invention adopts an external standard method to correct the element fractionation effect and the quality discrimination effect of the instrument on the isotope, namely, the isotope is obtained by calculating the real value and the real measured value of a standard sample146Nd/144And the actual ratio of Nd is substituted into the formula to calculate a correction factor, and further, the element fractionation effect in the laser ablation process and the quality discrimination effect generated in the test process are corrected and calculated. To obtain finally143Ndt/144NdtThe geological source of the sample is traced, and the evolution history of the shell mantle is further revealed.
The invention adopts Visual Basic language to write a highly intelligent automatic calculation program Nada, thereby saving the heavy manual calculation work in geological work, improving the work efficiency by more than one hundred times and providing better service for geological work.
The excerpt section computer program "Nada" code excerpt is as follows:
the technology related to the invention is already demonstrated and applied in the unit of the inventor and a certain college, has obvious effect and is commented consistently. The specific effect is shown in fig. 3 and 4.
By adopting the novel method provided by the embodiment of the invention, Nd isotope tests are carried out on apatite standard substances Durango (standard value: 0.512487 +/-0.000046), Mud Tank (standard value: 0.512361 +/-0.000111), sphene standard substance T3 (standard value: 0.512511 +/-0.000040) and T4 (standard value: 0.511676 +/-0.000056) in sequence, and the test results are respectively as follows: 0.512496 + -0.000073, 0.512311 + -0.000061, 0.512531 + -0.000019 and 0.511670 + -0.000052, the results are consistent with the recommended values within the error range, as shown in fig. 3(a), 3(b) and 4(a) and 4 (b).
Example 2:
the new method is adopted to research the granite of a certain gold ore, Nd isotope analysis is carried out on monazite minerals in the rock, so as to trace the magma source region of the granite and further analyze the cause of the gold ore. The analysis process is the same as that of example 1, the results are shown in fig. 5(a) -5 (c), as shown in the figure, the test results obtain the result with high precision, the value of epsilon Nd (t) of the Yangshan gold mine occurrence rock mass can be calculated according to the test results to be-3.7, the age of the two-stage mode is 1130 million years, and according to geological knowledge, the rock mass mother rock pulp is derived from the activation of the underground crust material formed 1130 million years ago.
It should be noted that the embodiments of the present invention can be realized by hardware, software, or a combination of software and hardware. The hardware portion may be implemented using dedicated logic; the software portions may be stored in a memory and executed by a suitable instruction execution system, such as a microprocessor or specially designed hardware. Those skilled in the art will appreciate that the apparatus and methods described above may be implemented using computer executable instructions and/or embodied in processor control code, such code being provided on a carrier medium such as a disk, CD-or DVD-ROM, programmable memory such as read only memory (firmware), or a data carrier such as an optical or electronic signal carrier, for example. The apparatus and its modules of the present invention may be implemented by hardware circuits such as very large scale integrated circuits or gate arrays, semiconductors such as logic chips, transistors, or programmable hardware devices such as field programmable gate arrays, programmable logic devices, etc., or by software executed by various types of processors, or by a combination of hardware circuits and software, e.g., firmware.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The method for analyzing the neodymium isotope in the rare earth-rich neodymium element mineral is characterized in that a laser ablation system and an inductively coupled plasma mass spectrometer are used for collecting mass quantity signals in a standard sample and an unknown sample;
of Sm in the sample based on the collected mass number signals144Sm isotope pair144Interference of Nd147And subtracting the signal of Sm and the isotope natural abundance of element Sm.
2. The method for analyzing neodymium isotopes in rare earth-rich neodymium element minerals as claimed in claim 1, wherein signals of 142,143,144,145,146,147 and 149 in mass numbers in a standard sample and an unknown sample are collected;
the homogeneous allotropic element interference deduction calculation formula of the method for analyzing the neodymium isotope in the rare earth-rich neodymium element mineral is as follows:
144Smt=144Smm-[147Smm×(144SmM/147SmM)];
wherein t represents the true value, M represents the measured value, and M represents the natural abundance of the isotope.
3. The method for analyzing the neodymium isotope in the rare earth-neodymium-rich mineral according to claim 1, wherein the correction calculation of the isotope fractionation in the test process of the method for analyzing the neodymium isotope in the rare earth-neodymium-rich mineral complies with an exponential fractionation law, and the formula is as follows:
β=ln(Rm/Rt)/ln(MA/MB);
wherein β is a mass discrimination correction coefficient, Rm is an actual measurement ratio, Rt is a true ratio, MA is an accurate mass number of the isotope a, and MB is an accurate mass number of the isotope B; isotopic fractionation of Sm using beta147Sm/149Sm is corrected, and isotope fractionation of Nd element adopts beta146Nd/144Nd is corrected.
4. The method for analyzing Nd isotope in mineral rich in Nd according to claim 1, wherein the method for analyzing Nd isotope in mineral rich in Nd uses external standard method to correct fractionation effect of elements and discrimination effect of quality of isotope by instrument, i.e. real value and measured value of standard sample are calculated146Nd/144Substituting the actual ratio of Nd into a formula to calculate a correction factor, and further correcting and calculating an element fractionation effect in the laser ablation process and a quality discrimination effect generated in the test process; to obtain finally143Ndt/144NdtThe geological source of the sample is traced, and the evolution history of the shell mantle is further revealed.
5. A computer arrangement, characterized in that it comprises a memory and a processor, the memory storing a computer program which, when executed by the processor, causes the processor to carry out the steps of the method of analysis of neodymium isotopes in a rare earth-neodymium element-rich mineral according to any one of claims 1 to 4.
6. A computer-readable storage medium storing a computer program which, when executed by a processor, causes the processor to perform the steps of the method of analyzing a neodymium isotope in a rare earth-rich neodymium element mineral according to any one of claims 1 to 4.
7. An information data processing terminal, characterized in that the information data processing terminal is used for realizing the method for analyzing the neodymium isotope in the rare earth-rich neodymium element mineral according to any one of claims 1 to 4.
8. A tracing system for geological source of neodymium isotope rich in neodymium in rare earth neodymium minerals, which implements the method for analyzing neodymium isotope in rare earth neodymium minerals according to any one of claims 1 to 4, is characterized in that the tracing system for geological source of neodymium isotope rich in neodymium comprises:
the Nd Calibration module is used for element fractionation, quality discrimination and interference correction calculation and has the functions of screening and prompting abnormal data;
the data Filter module is used for automatically processing abnormal data, filtering the abnormal data of the abnormal signal of each laser ablation point, deleting the data with the difference of more than 2.5 times of standard error from the signal mean value according to the filtering principle, acquiring 200 signal data for each laser ablation point, prompting a user to manually check the data when the deletion amount is more than or equal to one third, and analyzing the specific reason of the abnormality;
nd result table module for calculating beta147Sm/149Sm、β146Nd/144Nd、147Sm/144Nd n、143Nd/144Nd n、145Nd/144The value of Nd n, n being normalized, and the normalized value, and formatting the result.
9. A method for analyzing neodymium isotopes in rock by using a thermal ionization mass spectrometry is characterized by comprising the method for analyzing neodymium isotopes in the rare earth-rich neodymium element mineral according to any one of claims 1 to 4.
10. A method for analyzing neodymium isotopes in rocks by a multi-receiving plasma mass spectrometer is characterized by comprising the method for analyzing neodymium isotopes in rare earth-rich neodymium element minerals according to any one of claims 1 to 4.
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