CN100483101C - Method for eleminating interference of cyanate radical in boron isotope thermal ionization mass pectrum detecting - Google Patents
Method for eleminating interference of cyanate radical in boron isotope thermal ionization mass pectrum detecting Download PDFInfo
- Publication number
- CN100483101C CN100483101C CN 03134621 CN03134621A CN100483101C CN 100483101 C CN100483101 C CN 100483101C CN 03134621 CN03134621 CN 03134621 CN 03134621 A CN03134621 A CN 03134621A CN 100483101 C CN100483101 C CN 100483101C
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- CN
- China
- Prior art keywords
- ion
- cno
- ionization mass
- thermal ionization
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 20
- 101100328463 Mus musculus Cmya5 gene Proteins 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000176 thermal ionisation mass spectrometry Methods 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000452 restraining effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 34
- 239000000523 sample Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009957 hemming Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a method for eliminating cyanic acid radical disturbance in boron isotope thermal ionization mass spectrosoopy, which includes following steps: when using thermal ionization mass spectroscopic detection coat, the restraining agent and boron isotope are coated on the sample according to any proportion to carry on boron isotope detection; the method in the invention is to restrain the synthesis of CNO- and Cs2CNO+ion and eliminate the disturbance of CNO- and CS2CNO+ion to boron isotope detection.
Description
Technical field
The present invention relates to a kind of boron istope mass spectroscopy technology, the removing method that cyanate radical disturbed during especially a kind of boron istope thermal ionization mass spectrometry (tims) was measured.
Background technology
Nature boron has two kinds of stable isotopes,
10B and
11B, owing to have sizable relative mass poor (reaching 8.70%) between them, the nature boron istope can produce big isotope fractionation, this isotope fractionation will write down the information of chemical geological process to a great extent, so boron istope has obtained in cosmology, geology, mineralogy and geochemical a lot of field using widely.These are used the mensuration that the high precision boron istope is formed and have higher requirement.The mensuration that boron istope is formed has several different methods, and the thermal ionization mass spectrometry (tims) method is still the highest, the most widely used method of present mensuration boron istope composition precision.The thermal ionization mass spectrometry (tims) method that boron istope is formed has two kinds of positive thermal ionization and negative thermal ionizations.Based on Cs
2BO
2 +The positive thermal ionization mass spectrometry (tims) method of ion is at first to be set up by people such as Spivak in 1986, adopts graphite to be coated with the sample technology by the present patent application people Xiao Yingkai afterwards and improves improved Cs
2BO
2 +Obtained in the present world wide of ion method to use widely, become current mensuration boron istope and form the highest method of precision.But studies show that afterwards can induce to produce Cs in the presence of graphite
2CNO
+Ion, this ion and Cs
2BO
2 +Ion produces mass spectra peak at m/e 308 and 309 places simultaneously, but because Cs
2CNO
+Ion and Cs
2BO
2 +Ion produces mass spectra peak at m/e 308 and 309 places relative intensity differs and reaches nearly thousand times, so Cs
2CNO
+The mensuration that the existence of ion is formed boron istope produces serious disturbance, makes mensuration
11B/
10B ratio is seriously on the low side.Based on BO
2 -The negative thermal ionization mass spectrometry (tims) method of ion obtains to use in the boron istope composition measuring because detection sensitivity is high, but CNO
-The generation of ion equally can be to BO
2 -Ion produces the stack at peak, the boron istope composition measuring is produced serious the interference, makes mensuration equally
11B/
10B ratio is seriously on the low side.CNO
-And Cs
2CNO
+The micro-nitrate of introducing in that exist in the generation of ion and the sample or the specimen preparation process and organism etc. are relevant, so will remove interference components such as nitrate and organism as much as possible in the specimen preparation.But practical experience shows that the introducing of nitrate and organic matter etc. can not be avoided CNO fully
-And Cs
2CNO
+The interference of ion will might occur at any time.CNO during boron istope is measured
-And Cs
2CNO
+The isobary of ion disturbs to have become and hinders the key that boron istope is measured the further raising of precision, has caused World Science man's great attention.As in order to eliminate CNO
-Interference, Hemming etc. have taked multinomial measure to remove organic matter in the specimen preparation process, uses such as Liu do not contain the compound of nitrate radical as BO
2 -The emission of ions agent, but these measures fail fundamentally to eliminate CNO
-And Cs
2CNO
+As if the interference that the ion pair boron istope is measured is felt simply helpless to solving this difficult problem at present in the world, does not have highly effective solution.
Summary of the invention
The above removes denitrification when leaning against specimen preparation or organic way is eliminated CNO
-And Cs
2CNO
+The interference that the ion pair boron istope is measured is not fully reliably, because nitrate or organic introducing are at random sometimes, and CNO
-And Cs
2CNO
+The generation of ion can not be avoided fully.At nature, contain CNO
-The compound of ion is extremely micro-, CNO in boron istope is measured
-And Cs
2CNO
+The appearance of ion is instant synthetic in ion gun under specific condition, therefore eliminates CNO
-And Cs
2CNO
+It is to suppress CNO that the ion pair boron istope is measured the most basic way of disturbing
-And Cs
2CNO
+Synthesizing of ion.
The objective of the invention is to set up inhibition CNO
-And Cs
2CNO
+The method that ion is synthetic is thoroughly eliminated CNO
-And Cs
2CNO
+The interference of the isobary of ion pair boron istope composition measuring.
Purpose of the present invention can realize by following measure:
The removing method that cyanate radical disturbed during a kind of boron istope thermal ionization mass spectrometry (tims) was measured comprises the steps: when utilizing thermal ionization mass spectrometry (tims) to measure to be coated with sample inhibitor is coated in by arbitrary proportion with the boron istope sample and carries out the boron istope composition measuring on the sample band.
Described inhibitor is a high-purity phosphoric acid.
The present invention has following advantage compared to existing technology:
The present invention utilizes inhibitor, when being coated with sample this inhibitor is coated on the sample band with sample, and the existence of this inhibitor can suppress CNO effectively
-And Cs
2CNO
+Synthesizing of ion, the measurement result that boron istope is formed raises, and approaches normal measured value.
In the boron istope composition measuring, adopt NIST SRM 951 H usually
3BO
3As standard, adopt Na
2BO
2 +Ion is proofreaied and correct NIST SRM 951 H of mass spectrometric determination
3BO
3Absolute standard
11B/
10The B value is 4.04362 ± 0.00137
7But because graphite-Cs is adopted in the influence of systematic error
2BO
2 +Ion technology is measured
11B/
10B ratio is 4.05037 ± 0.00014
3, when having nitrate to exist, mensuration
11B/
10It is on the low side a lot of that B odds ratio 4.05037 is wanted, and its degree that departs from increases with the increase of nitrate amount, as at 1 μ g and 5.7 μ g NO
3 -Exist down, employing is measured
11B/
10B ratio is respectively 3.65543 and 3.88324, in the presence of enough inhibitor, mensuration
11B/
10B ratio brings up to 4.06099 and 4.04873 respectively.Adopt BO
2 -When the negative ion mass spectrum method is measured, with La (NO)
3Do that cast charge measures NISTSRM951
11B/
10B ratio is 3.98970, is starkly lower than standard value 4.04362, shows NO
3 -Exist significantly and disturb.In the presence of a certain amount of inhibitor, mensuration
11B/
10B ratio rises to 4.04703 and 4.05500, approaches to adopt graphite-Cs
2BO
2 +Ion technology is measured
11B/
10B ratio shows that the adding of inhibitor can be eliminated NO effectively
3 -Interference.
Concrete embodiment
Embodiment one:
Adopt suitable molten (melting) agent and boron special efficacy ion exchange resin that the boron in the sample is extracted, and carry out purifying, be prepared into the aqueous solution that contains a certain amount of boron.In positive thermal ionization mass spectrometry (tims) method is measured, the graphite of about 100 μ g is coated in a vacuum on 1 hour tantalum metal tape of heating under the 3A, add the sample solution that contains about 1 μ g boron again, the concentration that adds about 1 μ l at last is 1% high-purity phosphoric acid, after the electric current oven dry of logical 1A, the mass spectrograph ion gun of packing into after the ion gun vacuum reaches requirement, is 309 and 308 to sentence the peak and jump the mode of sweeping and measure quasi-molecular ions intensity at m/e.In the presence of phosphoric acid, Cs
2CNO
+Ion is inhibited fully, is that 309 and 308 places have only Cs respectively at m/e therefore
2 11BO
2 +And Cs
2 10BO
2 +Two kinds of quasi-molecular ions can directly calculate
11B/
10B ratio.
Embodiment two:
In negative thermal ionization mass spectrometry (tims) method is measured, the sample solution that will contain about 0.1 μ g boron is coated in a vacuum on 1 hour rhenium metal tape of heating under the 4A, the concentration that adds about 1 μ l at last is 1% high-purity phosphoric acid, after the electric current oven dry of logical 1.5A, the mass spectrograph ion gun of packing into, after the ion gun vacuum reaches requirement, be 43 and 42 to sentence the peak and jump the mode sweep and measure quasi-molecular ions intensity at m/e.In the presence of phosphoric acid, CNO
-Ion is inhibited fully, is that 43 and 42 places have only respectively at m/e therefore
11BO
2 -With
10BO
2 -Two kinds of quasi-molecular ions can directly calculate
11B/
10B ratio.
Claims (1)
1, the removing method that cyanate radical disturbed during a kind of boron istope thermal ionization mass spectrometry (tims) was measured comprises the steps: when utilizing thermal ionization mass spectrometry (tims) to measure to be coated with sample inhibitor and boron istope sample be coated on the sample band and measures; Described inhibitor is a phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03134621 CN100483101C (en) | 2003-09-17 | 2003-09-17 | Method for eleminating interference of cyanate radical in boron isotope thermal ionization mass pectrum detecting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03134621 CN100483101C (en) | 2003-09-17 | 2003-09-17 | Method for eleminating interference of cyanate radical in boron isotope thermal ionization mass pectrum detecting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1598555A CN1598555A (en) | 2005-03-23 |
| CN100483101C true CN100483101C (en) | 2009-04-29 |
Family
ID=34659046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03134621 Expired - Fee Related CN100483101C (en) | 2003-09-17 | 2003-09-17 | Method for eleminating interference of cyanate radical in boron isotope thermal ionization mass pectrum detecting |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100483101C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102062755B (en) * | 2010-10-18 | 2012-10-24 | 南京大学 | Method for determining boron isotopic composition with static double-receiving method by positive thermal ionization mass spectrometry |
| WO2012153704A1 (en) * | 2011-05-10 | 2012-11-15 | 株式会社ボナック | Process for preparing phosphate compound bearing isotope |
| CN103487497B (en) * | 2013-09-30 | 2016-03-23 | 中国核动力研究设计院 | A kind of boron isotope abundance measuring method using carbon nano-tube as emission of ions agent |
| CN106770610A (en) * | 2016-12-12 | 2017-05-31 | 中核北方核燃料元件有限公司 | A kind of abundance measurement method of boron 10 in boron and compound |
| CN108267497A (en) * | 2016-12-30 | 2018-07-10 | 核工业北京地质研究院 | Thermal ionization flight time mass spectrum measures the analytical equipment and method of boron istope |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253660A (en) * | 1997-03-14 | 2000-05-17 | 乔治华盛顿大学 | Device for continuous isotope ratio monitoring following fluorine based chemical reactions |
| JP2001324427A (en) * | 2000-05-16 | 2001-11-22 | Nippon Steel Corp | High-precision analysis method for boron in steel |
| JP2002257787A (en) * | 2001-03-05 | 2002-09-11 | Toshiba Ceramics Co Ltd | Determination of trace amount of boron |
-
2003
- 2003-09-17 CN CN 03134621 patent/CN100483101C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253660A (en) * | 1997-03-14 | 2000-05-17 | 乔治华盛顿大学 | Device for continuous isotope ratio monitoring following fluorine based chemical reactions |
| JP2001324427A (en) * | 2000-05-16 | 2001-11-22 | Nippon Steel Corp | High-precision analysis method for boron in steel |
| JP2002257787A (en) * | 2001-03-05 | 2002-09-11 | Toshiba Ceramics Co Ltd | Determination of trace amount of boron |
Non-Patent Citations (5)
| Title |
|---|
| SO42-、NO3-对氯同位素测定的干扰及其消除. 肖应凯等.盐湖研究，第9卷第2期. 2001 * |
| 元素同位素质谱测定新房法及其应用研究. 肖应凯等.盐湖研究，第6卷第2-3期. 1998 * |
| 有孔虫中硼的分离及其正热电离质谱法测定. 张崇耿等.分析化学，第31卷第4期. 2003 * |
| 负热电离质谱法测定黄土钙结核酸溶相硼同位素. 刘卫国等.海洋地质与第四纪地质，第22卷第3期. 2002 * |
| 高精度热电离质谱法测定铟同位素. 肖应凯等.分析化学，第20卷第4期. 1992 * |
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| Publication number | Publication date |
|---|---|
| CN1598555A (en) | 2005-03-23 |
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