JP2007170915A - Mass spectrum analysis method excluding obstruction of salting agent - Google Patents

Mass spectrum analysis method excluding obstruction of salting agent Download PDF

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JP2007170915A
JP2007170915A JP2005366692A JP2005366692A JP2007170915A JP 2007170915 A JP2007170915 A JP 2007170915A JP 2005366692 A JP2005366692 A JP 2005366692A JP 2005366692 A JP2005366692 A JP 2005366692A JP 2007170915 A JP2007170915 A JP 2007170915A
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thorium
uranium
analysis
sample solution
nitrate
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JP2005366692A
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Yutaka Hayashibe
Satoru Mizuno
Hiroshi Ozawa
洋 小沢
豊 林部
哲 水野
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Mitsubishi Materials Corp
三菱マテリアル株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an analysis method or a sample preparing method that exclude obstruction of salting agents in mass spectral analysis, using the salting agent which enhances adsorption amounts of a minor components. <P>SOLUTION: In a method for making a trace amount of uranium and thorium, contained in an acidic sample liquid, adsorbed to collect them and eluting both the uranium and thorium and then subjecting them to mass spectral analysis, calcium salt of the same acid as the sample liquid is used as the salting agent for enhancing the adsorption amount of uranium and thorium. For example, a nitric acid type sample liquid, to which calcium nitrate has been added as the salting agent, is passed through ion exchange resin or a filter, to adsorb uranium and thorium, and the uranium and thorium are subsequently made to elute, to perform mass spectral analysis due by ICP-MS. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an analysis method or sample preparation method capable of simultaneously adsorbing uranium and thorium and eliminating interference with a salting-out agent in mass spectral analysis using a salting-out agent that increases the adsorption amount of a trace component. The analysis method of the present invention is useful as a method for rapidly analyzing uranium / thorium contained in various materials such as electronic materials, soil, geochemical samples such as sediment and surface water, and waste.
Since uranium / thorium, which is an α emitter contained in a high-purity electronic material, causes soft errors, it needs to be eliminated as much as possible, and an analysis technique for evaluating it is required. Generally, uranium / thorium is measured by absorptiometry, ICP-AES (inductively coupled plasma atomic emission spectrometer), ICP-MS (inductively coupled plasma mass spectrometer), etc., but uranium / thorium is very small. The coexisting main components interfere with the measurement of uranium / thorium, which is the object of analysis, and measurement is performed by separating and concentrating uranium / thorium. Conventional common uranium / thorium separation and concentration methods include ion exchange and solvent extraction methods. However, since uranium and thorium have different distribution behavior for ion-exchange resin and distribution behavior in solvent, it is usually necessary to treat uranium and thorium separately, so analysis time is long and analysis operation is complicated. There is a problem.
On the other hand, a method is known in which uranium / thorium contained in manganese nodules is simultaneously adsorbed and analyzed. In this method, magnesium nitrate is added to a sample solution in which manganese nodules are dissolved in nitric acid to form uranium / thorium nitrate complex ions, which are simultaneously adsorbed on an anion exchange resin, and then thorium is mixed with 6 molar hydrochloric acid and uranium. Are eluted with 0.1 molar hydrochloric acid, a light-absorbing agent (Arsenazo III) is added to the eluted liquid, and quantitative analysis is performed by absorptiometry (Non-patent Document 1).
However, since this analysis method uses a high concentration of magnesium nitrate as a salting-out agent, it is not suitable for mass spectral analysis such as ICP-MS analysis. This is because ICP-MS analysis is performed under an argon plasma gas, so that magnesium that has a mass number different from that of argon remains in the device, causing spectral interference, and keeping the device healthy. This is because it becomes difficult.
In addition, as an analysis method of uranium and thorium by ICP-MS, for example, aluminum or an alloy thereof is dissolved in hydrochloric acid, and a mixed solution of tributyl phosphate and an organic solvent (cyclohexane or a mixture thereof) is added to the solution, A method is known in which uranium and thorium are simultaneously extracted into an organic solvent, water or 4N or less mineral acid is added to the extract to back-extract uranium and thorium, and this is measured by ICP-MS ( Patent Document 1). However, since this method is a solvent extraction method, there is a problem that the amount of organic solvent and reagents used is large compared to the ion exchange method, and the environmental load is large.
"Anion-Exchange System in Magunesium Nitrate Media Application to Chemical Analysis of Manganese Nodules for Thorium and Uranium" Fresenius Z. Anal. Chem. Vol. 300 Page.107-111: (1980) Author: Rokuro kuroda and Tatsuya Seki Japanese Patent Laid-Open No. 04-9663
The present invention solves the above-mentioned problems in the conventional analysis method, and eliminates interference of a salting-out agent by using, for example, calcium nitrate as a salting-out agent of a trace component, and simultaneously analyzes uranium and thorium. The present invention provides a mass spectrum analysis method and a sample preparation method thereof.
The present invention relates to a mass spectrum analysis method having the following configuration.
(1) In the method of adsorbing and collecting a small amount of uranium and thorium contained in an acidic sample solution, and eluting it to analyze the mass spectrum, it is the same as the sample solution as a salting-out agent for increasing the adsorption amount of uranium and thorium. A mass spectrum analysis method using a calcium salt of an acid.
(2) Using calcium nitrate as a salting-out agent, passing a nitrate sample solution to which calcium nitrate has been added through an ion exchange resin or filter to adsorb uranium and thorium in the sample solution, and then uranium and thorium The analysis method according to the above (1), wherein the mass spectrum analysis is performed by eluting
(3) In the analytical method described in either (1) or (2) above, a nitrate sample solution to which calcium nitrate has been added is passed through a disk filter to adsorb a small amount of uranium and thorium to the disk filter. And analyzing the mass spectrum by ICP-MS with eluting the uranium and thorium.
(4) In the analytical method described in any one of (1) to (3) above, a nitrate sample solution to which calcium nitrate has been added is passed through an ion exchange resin or a filter, and uranium and thorium in the sample solution are passed. Method for performing mass spectrometry by adsorbing uranium and then eluting uranium and thorium separately.
(5) A mass spectrum analysis method for analyzing bismuth together with uranium and thorium in the analysis method according to any one of (1) to (4) above.
In the analysis method of the present invention, a calcium salt of the same kind of acid as the sample solution is used as a salting-out agent, and this is added to the acidic sample solution to adsorb uranium and thorium. In addition, the amount necessary for the analysis can be collected by efficiently adsorbing them, and the analysis can be performed with high accuracy.
Specifically, the analysis method of the present invention uses, for example, calcium nitrate as a salting-out agent, which is added to a nitrate sample solution, and uranium and thorium contained in the sample solution are added to an ion exchange resin or a disk filter. This is a method of absorbing and collecting and performing mass spectrum analysis. Calcium used as a salting-out agent has a mass number of 40 and has the same mass number as argon, which is a plasma gas used for ICP mass spectrometry. Therefore, it does not interfere with the mass spectrum due to ion interference and performs high-precision analysis. be able to. Moreover, since no spectral interference occurs, the apparatus can be maintained soundly. In addition, the use of nitrate reduces the contribution of adsorption of transition metal elements (iron, copper), aluminum, etc., which frequently interfere with analysis as coexisting components, and improves selectivity to uranium, thorium and bismuth. Can do.
In addition, the analysis method of the present invention can directly measure because the salting-out agent mixed in can be reduced to a level that does not affect the measurement by using a disk filter having a very small void volume. Furthermore, in order to increase the concentration rate, it is possible to measure by substantially removing the salting-out agent by washing the disk filter with mineral acid (such as acetic acid or nitric acid) alone or mixed.
The analysis method of the present invention is a particularly effective analysis method when a rapid analysis result is required because the uranium / thorium content of various electronic materials can be quickly known. Specifically, in the conventional analysis method, since the distribution behavior of uranium and thorium to the ion exchange resin is different, it is necessary to treat them separately, and accordingly, evaporation to dryness, ion exchange and It is necessary to perform organic substance decomposition after the solvent extraction. For this reason, for example, it takes 4 days to analyze 5 samples (n = 3). On the other hand, according to the analysis method of the present invention, the analysis time can be shortened to one day. Therefore, the analysis method of the present invention is effective for on-site process management and quality control that require quick response such as screening for environmental purification work and complaint handling.
Moreover, since the analysis method of the present invention can selectively separate and concentrate uranium / thorium from many matrix components, it can be applied to various samples. Furthermore, the analysis method of the present invention has an advantage of not using an organic solvent having a high environmental load used in the solvent extraction method.
The analysis method of the present invention is a method of adsorbing and collecting a small amount of uranium and thorium contained in an acidic sample solution, and eluting it to analyze the mass spectrum. A mass spectral analysis method using a calcium salt of an acid of the same type as a sample solution.
Specifically, the analysis method of the present invention uses, for example, calcium nitrate as a salting-out agent, which is added to a nitrate sample solution, and uranium and thorium contained in the sample solution are added to an ion exchange resin or a disk filter. This is a method of absorbing and collecting and performing mass spectrum analysis.
When a small amount of uranium and thorium contained in a sample solution is adsorbed on an ion exchange resin and collected, and mass spectrometry is performed, the adsorption rate of uranium and thorium generally differs depending on the liquidity of the sample solution. In the solution, the adsorption rate of uranium is high but the adsorption rate of thorium is low. In the nitrate sample solution, the adsorption rate of uranium is low, but the adsorption rate of thorium is high. For this reason, in the conventional analysis method, there is a problem that the analysis operation is troublesome because the uranium and thorium are individually adsorbed by changing the liquidity of the sample solution.
The analysis method of the present invention, for example, maintains a high adsorption rate of thorium using a sample solution as a nitrate solution, and increases the adsorption rate of uranium by adding calcium nitrate as a salting-out agent to the nitrate sample solution. And thorium can be adsorbed simultaneously. As described above, when magnesium nitrate is used, interference on the mass spectrum caused by magnesium occurs, so magnesium nitrate is not suitable.
FIG. 1 shows an example of the analysis method or sample preparation method of the present invention. In this example, an ion exchange resin is used, and an anion exchange resin 11 is sealed in a cylindrical cartridge 10. As the anion exchange resin, a commercially available product (for example, trade name: Bio-Rad AG1-X8, 1 g) can be used. Hydrochloric acid is poured into this to clean the inside. For example, dilute hydrochloric acid is used as the washing hydrochloric acid, and the inside is washed by injecting it twice in 10 ml portions.
Next, conditioning is performed by injecting a calcium salt solution of the same kind of acid as the sample solution into the cartridge. For example, a calcium nitrate solution is used for a nitrate sample solution. Preferably, the same liquid solution as the sample solution to which the calcium salt is added is used. Specifically, for example, conditioning is performed by passing a mixed solution of 4M calcium nitrate [Ca (NO 3 ) 2 ] -0.1M nitric acid.
On the other hand, a sample solution containing uranium / thorium is prepared to have the same liquidity as the above conditioning. Specifically, for example, calcium nitrate and nitric acid as necessary are added to the sample solution, and the liquidity of the sample solution is adjusted to, for example, 4M calcium nitrate [Ca (NO 3 ) 2 ] -0.1M nitric acid. To do. This sample solution is passed through the cartridge 10 to adsorb the uranium / thorium contained in the sample solution to the anion exchange resin 11. The flow rate may be about 1 ml per minute.
After passing the sample solution, nitric acid is injected into the cartridge 10 to clean the inside, and the remaining calcium is washed away. For example, 8M nitric acid may be used as the cleaning nitric acid. Next, hydrochloric acid is injected into the cartridge 11 to elute uranium / thorium adsorbed on the anion exchange resin. The hydrochloric acid used as the eluent may be about 20 ml of diluted hydrochloric acid. This can be injected at a rate of 3 ml per minute. An eluent containing uranium / thorium is introduced into an ICP-MS or the like to perform mass spectrum analysis.
FIG. 2 shows the analysis method or sample preparation method of the present invention using a disk filter. A disk filter 21 is enclosed in a cylindrical glass funnel 20. As the disc filter, a commercially available product (for example, trade name Empore Anion-SR manufactured by 3M) can be used. After the disc 21 is set, alcohol is injected to swell the disc 21. As the alcohol, methyl alcohol or the like may be used. Further, hydrochloric acid is injected to clean the inside. For example, dilute hydrochloric acid is used as the washing hydrochloric acid, and the inside is washed by injecting it twice in 10 ml portions.
Next, conditioning is performed by injecting a calcium salt solution of the same kind of acid as the sample solution into the funnel. For example, a calcium nitrate solution is used for a nitrate sample solution. Preferably, the same liquid solution as the sample solution to which the calcium salt is added is used. Specifically, for example, 4M calcium nitrate [Ca (NO 3 ) 2 ] solution is passed for conditioning.
On the other hand, a sample solution containing uranium / thorium is prepared to have the same liquidity as the above conditioning. Specifically, for example, calcium nitrate and nitric acid as needed are added to the sample solution, and the liquidity of the sample solution is adjusted to contain, for example, 4M calcium nitrate [Ca (NO 3 ) 2 ]. . This sample solution is passed through the funnel 20 and uranium / thorium contained in the sample solution is adsorbed on the disk 21.
After passing the sample liquid, the disk filter 21 is replaced with a new glass funnel 20 and a glass support base 22, and hydrochloric acid is injected into the disk filter 21 to elute uranium / thorium. As an eluent, about 2.5 ml of diluted hydrochloric acid may be injected per minute. An eluent containing uranium / thorium is introduced into an ICP-MS or the like to perform mass spectrum analysis.
In the above method, when using an anion exchange resin or a disk filter, the elution step may elute uranium and thorium at the same time, or separate uranium and thorium separately using different eluents. It may be eluted.
In the mass spectrum analysis by ICP-MS, the analysis accuracy usually decreases when the element concentration of the sample liquid becomes 1000 ppm or more. However, in the analysis method of the present invention using a disk filter, the concentration of the salting-out agent is greatly reduced. Specifically, since the calcium concentration can be suppressed to less than 1000 ppm, high-accuracy mass spectrum analysis can be performed by ICP-MS.
A sample preparation procedure for analyzing uranium / thorium in rocks by the analysis method of the present invention is shown in FIG. As shown in the figure, sodium peroxide (Na 2 O 2 ) is added to the sample for melting and decomposition, and nitric acid is further added to leach uranium / thorium. The sample solution is prepared by measuring the volume of this leachate, separating and concentrating it, and further adding 4M calcium nitrate and dissolving by heating. This sample solution is passed through the anion exchange resin-containing cartridge shown in FIG. After passing, elution is performed by injecting an eluent of dilute hydrochloric acid, and a fixed volume of eluent containing uranium / thorium is introduced into ICP-MS, and mass spectrum analysis is performed based on the internal standard method. The results are shown in Table 1. The average of five measurements was uranium 96.2 ± 1.4%, thorium 95.4 ± 0.7%, and standard deviations were 0.7% and 1.2%, respectively. Results were obtained. Moreover, the analytical values obtained by the present invention agreed well with the analytical values obtained by the conventional method (Table 2).
Process diagram and apparatus diagram of the present invention using anion exchange resin Process diagram and apparatus diagram of the present invention using a disk filter Process drawing showing an embodiment of the present invention
Explanation of symbols
10-cartridge, 11-anion exchange resin, 20-glass funnel, 21-disc filter, 22-glass support base

Claims (5)

  1. In a method of absorbing and collecting a small amount of uranium and thorium contained in an acidic sample solution, and eluting the uranium and thorium to elute it, the salt of the same kind of acid as the sample solution is used as a salting-out agent to increase the adsorption amount of uranium and thorium. A mass spectrum analysis method using a calcium salt.

  2. Calcium nitrate is used as a salting-out agent, and the nitrate sample solution with calcium nitrate added is passed through an ion exchange resin or filter to adsorb uranium and thorium in the sample solution, and then elute the uranium and thorium. The analysis method according to claim 1, wherein mass spectrum analysis is performed.
  3. 3. The analysis method according to claim 1, wherein a nitrate sample solution to which calcium nitrate has been added is passed through a disk filter, and a small amount of uranium and thorium are adsorbed on the disk filter. An analysis method for performing mass spectrum analysis by ICP-MS after elution.
  4. 4. The analysis method according to claim 1, wherein a nitrate sample solution to which calcium nitrate has been added is passed through an ion exchange resin or a filter to adsorb uranium and thorium in the sample solution, and then uranium. And mass spectrometry by eluting thorium individually.
  5. 5. The analysis method according to claim 1, wherein bismuth is analyzed simultaneously with uranium and thorium.


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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101551357B (en) * 2009-02-26 2013-02-06 中国兵器工业集团第五三研究所 ICP-MS measuring method of trace metal impurities in high purity lead
CN103512773A (en) * 2012-06-25 2014-01-15 宝山钢铁股份有限公司 Self-cleaning liquid measurement cabin

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS5614942A (en) * 1979-07-18 1981-02-13 Hitachi Ltd Method and apparatus for determining amount of uranium
JPH049663A (en) * 1990-04-26 1992-01-14 Sumitomo Chem Co Ltd Analysis of uranium and thorium in aluminum or alloy thereof
JPH0666726A (en) * 1992-08-24 1994-03-11 Kawasaki Steel Corp Atomizing method for analysis sample
JPH08111203A (en) * 1994-10-13 1996-04-30 Jeol Ltd High resolution mass spectrometer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5614942A (en) * 1979-07-18 1981-02-13 Hitachi Ltd Method and apparatus for determining amount of uranium
JPH049663A (en) * 1990-04-26 1992-01-14 Sumitomo Chem Co Ltd Analysis of uranium and thorium in aluminum or alloy thereof
JPH0666726A (en) * 1992-08-24 1994-03-11 Kawasaki Steel Corp Atomizing method for analysis sample
JPH08111203A (en) * 1994-10-13 1996-04-30 Jeol Ltd High resolution mass spectrometer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JPN6010055139, 小沢洋,外3名, ""微量ウラン/トリウム簡易同時分析法"", 日本分析化学会第54年会講演要旨集, 20050831, p.250 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101551357B (en) * 2009-02-26 2013-02-06 中国兵器工业集团第五三研究所 ICP-MS measuring method of trace metal impurities in high purity lead
CN103512773A (en) * 2012-06-25 2014-01-15 宝山钢铁股份有限公司 Self-cleaning liquid measurement cabin

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