CN100348976C - Method for determining content of (18) 0 isotope in water - Google Patents
Method for determining content of (18) 0 isotope in water Download PDFInfo
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- CN100348976C CN100348976C CNB2004100893629A CN200410089362A CN100348976C CN 100348976 C CN100348976 C CN 100348976C CN B2004100893629 A CNB2004100893629 A CN B2004100893629A CN 200410089362 A CN200410089362 A CN 200410089362A CN 100348976 C CN100348976 C CN 100348976C
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Abstract
The present invention provides a method for determining the content of (18)<O> isotope in water. In the method, water sample and excessive guanidine hydrochloride react under a vacuum state, so that atoms of the (18)<O> isotope in the water sample are completely transferred to CO2 molecule, then, foreign gas except for CO2 in the gas generated during the reaction is removed through subzero refrigeration, and the content of the (18)<O> isotope in the CO2 is measured through a gas-phase isotope mass spectrometer to determine the content of the (18)<O> isotope in the water sample to be measured. The present invention is suited for measuring the content of (18)<O> isotopic within range of fully abundance in the water sample. The present invention requires little water sample and has the advantages of easy operation, good repetitiveness and high test precision, and provides a convenient, feasible, exact and reliable method for measuring the content of (18)<O> isotopic for national heavy oxygen water producing enterprises.
Description
Technical field
The present invention relates to a kind of branch folding method, in particularly a kind of water
18The assay method of O isotopic content.
Background technology
The oxygen element of occurring in nature has three kinds of stable isotopes, and its mass number is respectively 16,17,18, and note is done respectively
16O,
17O and
18O.Its abundance (atom content) in the natural water molecule is respectively,
16O:99.76 atom %;
17O:0.04 atom %;
18O:0.2 atom %.We comprise by the oxygen element of common indication
16O,
17O and
18O.Wherein
17O and
18O is called heavy oxygen isotope because they and
16The outside character of O is close, can substitute mutually and does not influence the physicochemical property of former material, is applied to many fields such as physical chemistry, biology, medicine and pharmacology, environmental science widely so can be used as tracer atom.Particularly in recent years, along with the science and technology and the raising of people's living standard, to the also increasing gradually of demand of the heavy oxygen isotope of component fundamental element oxygen.Especially at present show positron emission computerized tomography (PET) technology that the phase field occurs in nuclear medicine, more new more wide application prospect has been opened up in the application of heavy oxygen isotope.
The product form of heavy oxygen isotope is mainly heavy oxygen water, promptly
18The O isotopic content is higher than the water of its natural abundance.
At present, in the water
18Exchange process is adopted in the analysis of O isotopic abundance usually, and this method is measured and once needed consuming timely more than 24 hours, and length consuming time, anti-interference are poor, and repeatability is low, accuracy rate is low.And its to measure once spent water sample more, be generally several milliliters.And heavy oxygen water, particularly
18The heavy oxygen water price lattice of O abundance＞95 atom % are extremely expensive, utilize exchange process to measure in the water sample
18The O isotopic abundance was both inconvenient for the aquatic product of heavy oxygen enterprise, and cost dearly.
Summary of the invention
Purpose of the present invention is to overcome prior art and measures in the water
18The existing deficiency of the method for O isotopic content, provide a kind of simple and fast, convenient and practical, cheap, accurately and reliably in the water
18The assay method of O isotopic content.
The object of the present invention is achieved like this, earlier water sample to be determined (1～15 microlitre) is packaged in the kapillary, then kapillary is positioned in the reaction glass tube with guanidine hydrochloride, utilize the Vacuum Package sample preparation device of setting up to take out the interior air of dereaction glass tube, vacuum tightness in reacting glass tube is reduced to when 0.01～1.0Pa (absolute pressure), to react glass tube and seal, thereby avoid airborne CO
2Reaction result is exerted an influence.The kapillary that water sample is housed that then will seal in the reaction glass tube staves, water sample is fully contacted with guanidine hydrochloride, to react glass tube then is positioned in the muffle furnace, the control temperature is between 120～350 ℃, reacted 1～6 hour, make water sample and guanidine hydrochloride obtain fully, react completely, make in the water sample
18The O isotope atom is transferred to the CO that reaction generates fully
2Go in the molecule.After reaction finished the question response glass tube and is cooled to room temperature, will react glass tube, to be positioned over temperature be in-50～-100 ℃ of constant temperature liquid, utilizes freezing method to remove in the gas of reaction generation except that CO
2Outer foreign gas.Fracture then and react the end of glass tube, will be through the CO that purifies
2Gas injects the gas phase isotope mass spectrometer, and 44～49 peak intensity according to the gas phase isotope mass spectrometer is measured calculates CO
2In
18The isotopic content of O, thus get in the water outlet
18The isotopic content of O.
The present invention is applicable in the water sample in the full abundance scope
18The mensuration of O isotopic content, the required water sample amount of each mensuration only is several microlitres, has reduced about 1000 times with respect to common employed exchange process, and easy and simple to handle, good reproducibility, measuring accuracy height are for the aquatic product of China's heavy oxygen enterprise provides a kind of simple and feasible, accurately and reliably
18The assay method of O isotopic content.
Description of drawings
Fig. 1 is in the water of the present invention
18The synoptic diagram of the reaction glass tube that uses in the assay method of O isotopic content;
Fig. 2 is in the water of the present invention
18The Vacuum Package sample preparation schematic representation of apparatus of using in the assay method of O isotopic content.
Embodiment
With reference to Fig. 1, Fig. 1 is the synoptic diagram of the reaction glass tube that uses among the present invention.One end of reaction glass tube 1 is an opening end 11, and the other end is a drawing-down sealing end 12, and opening end is preset with a thin neck 13.In use, the kapillary 2 and the guanidine hydrochloride 3 that will be packaged with water sample are put into the reaction glass tube by opening end 11, and be after access Vacuum Package sample preparation device vacuumizes, that thin neck 13 envelopes are disconnected.Then can integral body place muffle furnace to add thermal response and place the cryogenic thermostat liquid bath freezing.Sample introduction before measuring fractures drawing-down sealing end 12.
With reference to Fig. 2, cooperate referring to Fig. 1.The Vacuum Package sample preparation device synoptic diagram of Fig. 2 for using among the present invention comprises reaction glass tube 1, gas phase isotope mass spectrometer 4, vacuum pump 5, constant temperature fluid bath 6, cryotrap 7, valve 81,82,83,84,85,86 and corresponding connecting tube shown in the figure.After reaction glass tube 1 installs the kapillary 2 and guanidine hydrochloride 3 that is packaged with water sample, it is inserted Vacuum Package sample preparation device, Open valve 81,82,83,86, valve-off 84,85, open vacuum pump 5, make reaction glass tube 1 internal pressure be reduced to 0.01～1.0Pa (absolute pressure) after, will react glass tube 1 and break from thin neck 13 envelopes, valve-off 81,82,86 stops vacuum pump 5.Take off the reaction glass tube 1, approved sample kapillary 2 is crashed through, water sample and guanidine hydrochloride are fully mixed after, to react glass tube 1 and be positioned in the muffle furnace, the control temperature was reacted 1～6 hour between 120～350 ℃, make water sample and guanidine hydrochloride obtain fully, react completely, make in the water sample
18The O isotope atom is transferred to the CO that reaction generates fully
2Go in the molecule.Then abundant reacted reaction glass tube 1 is positioned over temperature and is in-50～-100 ℃ the constant temperature fluid bath 6, utilize freezing method to remove the CO that removes that reaction generates
2The foreign gas that gas is outer. Open valve 84,85 then, and the drawing-down sealing end 12 of the reaction glass tube 1 that fractures will be through the CO that purifies
2Gas injects gas phase isotope mass spectrometer 4, and 44～49 peak intensity according to the gas phase isotope mass spectrometer is measured calculates CO
2In
18The isotopic content of O, thus get in the water outlet
18The isotopic content of O.
In conjunction with several specific embodiments method of the present invention is further described again below.
With 8 microlitre natural waters (
18The O abundance is 0.204%) inject kapillary, put into the reaction glass tube that guanidine hydrochloride has been housed then, be connected in the Vacuum Package sample preparation device, be evacuated to vacuum tightness and remain on about 0.01Pa, will react the thin neck envelope of glass tube and break.Again kapillary is crashed through, water sample is contacted with guanidine hydrochloride, put into muffle furnace then, in 250 ℃ of environment, kept 1 hour.After reaction finishes, the reaction glass tube is put into-70 ℃ constant temperature fluid bath, utilize freezing method to remove and react the CO that removes that generates
2The foreign gas that gas is outer.Then will be through the CO of freezing purification
2Inject the gas phase isotope mass spectrometer, measure 44～49 peak intensity, can calculate CO
2In the molecule
18The content of O isotope atom.Measurement result shows in this water sample
18The O isotopic content is 0.203%, and measuring error is 0.49%.
With 15 microlitres
18The O abundance is 10.6% standard water sample injection kapillary, puts into the reaction glass tube of having adorned guanidine hydrochloride then, is connected in the Vacuum Package sample preparation device, is evacuated to vacuum tightness and remains on about 0.1Pa, will react the thin neck envelope of glass tube and break.Again kapillary is crashed through, water sample is contacted with guanidine hydrochloride, put into muffle furnace then, in 120 ℃ of environment, kept 3 hours.After reaction finishes, the reaction glass tube is put into-50 ℃ constant temperature fluid bath, utilize freezing method to remove and react the CO that removes that generates
2The foreign gas that gas is outer.Then will be through the CO of freezing purification
2Inject the gas phase isotope mass spectrometer, measure 44～49 peak intensity, can calculate CO
2In the molecule
18The content of O isotope atom.Measurement result shows in this water sample
18The O isotopic content is 10.65%, and measuring error is 0.47%.
With 1 microlitre
18The O abundance is 86.8% standard water sample injection kapillary, puts into the reaction glass tube of having adorned guanidine hydrochloride then, is connected in the Vacuum Package sample preparation device, is evacuated to vacuum tightness and remains on about 0.01Pa, will react the thin neck envelope of glass tube and break.Again kapillary is crashed through, water sample is contacted with guanidine hydrochloride, put into muffle furnace then, in 300 ℃ of environment, kept 6 hours.After reaction finishes, the reaction glass tube is put into-100 ℃ constant temperature fluid bath, utilize freezing method to remove the foreign gas except that CO2 gas that reaction generates.Then will be through the CO of freezing purification
2Inject the gas phase isotope mass spectrometer, measure 44～49 peak intensity, can calculate CO
2In the molecule
18The content of O isotope atom.Measurement result shows in this water sample
18The O isotopic content is 86.64%, and measuring error is 0.19%.
With 6 microlitres
18The O abundance is 96.8% standard water sample injection kapillary, puts into the reaction glass tube of having adorned guanidine hydrochloride then, is connected in the Vacuum Package sample preparation device, and vacuum tightness remains on about 1.0Pa, will react the thin neck envelope of glass tube and break.Again kapillary is crashed through, water sample is contacted with guanidine hydrochloride, put into muffle furnace then, in 350 ℃ of environment, kept 5 hours.After reaction finishes, the reaction glass tube is put into-80 ℃ constant temperature fluid bath, utilize freezing method to remove and react the CO that removes that generates
2The foreign gas that gas is outer.Then will be through the CO of freezing purification
2Inject the gas phase isotope mass spectrometer, measure 44～49 peak intensity, can calculate CO
2In the molecule
18The content of O isotope atom.Measurement result is water sample for this reason
18The O isotopic content is 96.3%, and measuring error is 0.05%.
Claims (4)
1, in a kind of water
18The assay method of O isotopic content is characterized in that: may further comprise the steps:
A,
18The isotopic transfer of O
Small amount of water sample and excessive hydrochloric acid guanidine are added thermal response under vacuum state, make in the water sample
18The O isotope atom is transferred to CO fully
2In the molecule, its chemical equation is as follows:
(NH
2)
2C＝NH·HCl+2H
2O→CO
2+2NH
3+NH
4Cl；
B, CO
2Gas cleaning
Remove in the gas that reacts generation except that CO by cryogenic freezing
2Foreign gas in addition obtains pure CO
2Gas, the temperature of described cryogenic freezing are controlled between-50～-100 ℃;
C,
18The mensuration of O isotopic content
Will be through the CO that purifies
2Gas injects the gas phase isotope mass spectrometer and measures its molecule
18The content of O isotope atom, and extrapolate in the water sample thus
18The content of O isotope atom.
2, in the water according to claim 1
18The assay method of O isotopic content is characterized in that: the vacuum state described in the step a is absolute pressure 0.01～1.0Pa, and temperature of reaction is controlled between 120～350 ℃, and the reaction time was controlled between 1～6 hour.
3, in the water according to claim 1 and 2
18The assay method of O isotopic content is characterized in that: the cryogenic freezing temperature described in the step b is controlled between-50～-80 ℃.
4, in the water according to claim 3
18The assay method of O isotopic content is characterized in that: the cryogenic freezing temperature described in the step b is controlled between-50～-70 ℃.
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| CNB2004100893629A CN100348976C (en) | 2004-12-10 | 2004-12-10 | Method for determining content of (18) 0 isotope in water |
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| CN100348976C true CN100348976C (en) | 2007-11-14 |
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Families Citing this family (8)
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| CN102967661B (en) * | 2012-10-28 | 2014-09-10 | 中国食品发酵工业研究院 | Rapid determination method for oxygen stable isotope of ethanol in alcoholic beverage |
| CN102967678B (en) * | 2012-11-20 | 2014-08-13 | 中国食品发酵工业研究院 | Offline pretreatment device and method for simply measuring oxygen stable isotope ratio in water |
| CN105021732A (en) * | 2014-11-03 | 2015-11-04 | 中国食品发酵工业研究院 | Method for fast determination of oxygen isotope composition of water in beverage wine |
| CN106501048B (en) * | 2016-12-07 | 2019-04-09 | 中国地质科学院水文地质环境地质研究所 | A kind of preparation facilities of Diagnosis of Helicobacter pylori Infection test sample and the preparation method of test sample |
| CN106769346B (en) * | 2017-03-21 | 2020-02-07 | 中国科学院地质与地球物理研究所 | Method for analyzing hydrogen isotopes in water |
| CN109946407A (en) * | 2017-12-20 | 2019-06-28 | 核工业北京地质研究院 | A kind of mineral inclusion water sample extraction element for H isotope analysis |
| CN111268678A (en) * | 2020-03-12 | 2020-06-12 | 江苏华益科技有限公司 | Preparation method, device and application of high-abundance oxygen-18 carbon dioxide |
| CN113758991A (en) * | 2021-09-10 | 2021-12-07 | 北京善为正子医药技术有限公司 | Purity detection method of high-abundance oxygen-18 water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1112260A1 (en) * | 1982-07-16 | 1984-09-07 | Институт Геохимии И Физики Минералов Ан Усср | Method of extracting oxygen from solid inorganic substances |
| CN2476014Y (en) * | 2001-04-25 | 2002-02-06 | 西南石油学院 | Carbon. oxygen isotope analysis laser micro sampler |
-
2004
- 2004-12-10 CN CNB2004100893629A patent/CN100348976C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1112260A1 (en) * | 1982-07-16 | 1984-09-07 | Институт Геохимии И Физики Минералов Ан Усср | Method of extracting oxygen from solid inorganic substances |
| CN2476014Y (en) * | 2001-04-25 | 2002-02-06 | 西南石油学院 | Carbon. oxygen isotope analysis laser micro sampler |
Non-Patent Citations (2)
| Title |
|---|
| 天然光卤石(KMgCl3.6H2O)中结晶水的氧同位素效应研究 肖云.同位素，第8卷第3期 1995 * |
| 盐酸胍法测定磷酸盐中氧—18的含量 李文军，等.核化学与放射化学，第1期 1985 * |
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Owner name: SHANGHAI CHEMICAL RESEARCH INST; APPLICANT Free format text: FORMER OWNER: SHANGHAI CHEMICAL RESEARCH INST Effective date: 20060804 |
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Effective date of registration: 20060804 Address after: 200062 Shanghai Yunling Road No. 345 Applicant after: Shanghai Research Institute of Chemical Industry Co-applicant after: Shanghai Lianhong Isotope Technology Co., Ltd. Address before: 200062 Shanghai Yunling Road No. 345 Applicant before: Shanghai Research Institute of Chemical Industry |
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Address after: 200062 Shanghai Yunling Road No. 345 Co-patentee after: Shanghai Lianhong Isotope Technology Co., Ltd. Patentee after: Shanghai Chemical Research Institute Co., Ltd. Address before: 200062 Shanghai Yunling Road No. 345 Co-patentee before: Shanghai Lianhong Isotope Technology Co., Ltd. Patentee before: Shanghai Research Institute of Chemical Industry |
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