CN103675087A - Analytic method of oxygen isotopes in sulfate radicals - Google Patents
Analytic method of oxygen isotopes in sulfate radicals Download PDFInfo
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- CN103675087A CN103675087A CN201310706290.7A CN201310706290A CN103675087A CN 103675087 A CN103675087 A CN 103675087A CN 201310706290 A CN201310706290 A CN 201310706290A CN 103675087 A CN103675087 A CN 103675087A
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Abstract
The invention provides an analytic method of oxygen isotopes in sulfate radicals. The analytic method comprises the following steps: mixing a sample with graphite powder according to a predetermined ratio, putting a mixture into a reactor, and repeating for multiple times to prepare a plurality of reactors with the samples and the graphite powder; connecting the reactors to a vacuum pumping device for vacuum pumping; when the vacuum degree of a vacuum system reaches a predetermined value, forging the reactors by a flame gun respectively to form a plurality of independent vacuum sealed reactors; intensively reacting in the independent vacuum sealed reactors at the predetermined temperature for the predetermined time, and after reacting, cooling the independent vacuum sealed reactors; breaking off the independent vacuum sealed reactors in a vacuum state, collecting gas generated in reaction, and purifying the collected gas; performing oxygen isotope analysis on the obtained gas on a gas mass spectrometer. By the method, the analysis operation is accurate, the analysis speed is increased, and the continuous quick test of the oxygen isotopes in a large amount of the sulfate radicals is achieved.
Description
Technical field
The present invention relates to the analytical approach of stable isotope, relate to especially the analytical approach of oxygen isotope in sulfate radical.
Background technology
Sulfate is a kind of common minerals, is distributed widely among hypergene and endogenous cycle border such as ocean, river, lake, sediment, salt deposit, soil, weathering crust, atmosphere and hydrothermal deposit etc.
In sulfate radical, the research of oxygen isotope is more than 50 years.In sulfate radical, the research of oxygen isotope can solve many geological problems, for example, for to paleoenvironment, paleoclimate research; The research of the forming process of hydrothermal deposit; Research to the spike of the sulfate radical in underground water and formation mechanism; In modern environment, atmospheric pollution is as probing into of the formation mechanism of acid rain etc.
At present, in sulfate, the analytical approach of oxygen isotope has off-line analysis method and on-line analysis conventionally, wherein in off-line analysis method, first adopt chemical method that the oxygen in sulfate radical is converted into gas, then gas collection reaction being generated gets up to carry out mass spectrophotometry, thereby analyzes oxygen isotope in sulfate radical.Chemical method used mainly comprises fluoride process and carbon reduction method.Fluoride process has can directly measure δ
17the advantages such as O value, but the analysis process of the method is complicated, and the productive rate of oxygen is lower, and need to be to measured δ
18o proofreaies and correct with known standard model.Carbon reduction method be a kind of be reduced into carbon dioxide and measure carbon dioxide after sulfate being reacted with graphite under hot conditions in the analytical technology that forms of oxygen isotope.With respect to fluoride process, the reagent in the course of reaction of carbon reduction method does not have toxicity, and the productive rate of sulfate radical and the reacted carbon dioxide of graphite is higher, analysis process is simple, accurately and reliably, therefore, carbon reduction method is widely used in analyzing oxygen isotope in sulfate radical to analysis result.
Yet, in traditional off-line analysis method, normally sample is placed in a fixing reactor (as quartz ampoule), sample needs reaction in order one by one, and the different samples containing oxygen isotope all react in a reactor, often easily cause so-called memory effect, it is the impact that the oxygen isotope of its post-reacted sample is subject to the oxygen isotope of a sample, particularly, for the larger sample of oxygen isotope value difference, meanwhile, analysis speed is slower.Therefore,, along with the increase year by year of research testing requirement, be badly in need of a kind of continuous rapid analysis that can improve precision of analysis and analysis speed.
Summary of the invention
In order to solve problems of the prior art, the invention provides the analytical approach of oxygen isotope in a kind of sulfate radical, in this analytical approach, a corresponding reactor of sample, and a plurality of reactors concentrate under identical temperature conditions and react, thereby not only avoided oxygen isotope memory effect, also greatly improved the analysis speed of sample, realized continuous express-analysis.
The present invention uses carbon reduction method that the oxygen in sulfate radical is converted into gas, take containing sulfate radicals sample as barium sulphate be example, reaction principle is: BaSO
4+ 2C → BaS+2CO
2.
According to an aspect of the present invention, provide the analytical approach of oxygen isotope in a kind of sulfate radical, comprise the following steps:
(1) sample and dag be take to the ratio that weight ratio is 1: 2 and be uniformly mixed, then potpourri is packed in reactor, repeatedly abovementioned steps, prepares a plurality of reactors that sample and dag are housed;
(2) described a plurality of reactors are connected to vacuum withdraw device by silicone tube, open mechanical pump and diffusion pump and valve, vacuumize processing;
(3) by vacuum manometer, the vacuum tightness of vacuum system is monitored, when the vacuum tightness that monitors vacuum system when vacuum manometer reaches 0.01Pa, use flame gun respectively described reactor to be forged and taken off at distance described reactor opening 3-4cm place, form a plurality of independent vacuum sealed reactors;
(4) described a plurality of independent vacuum sealed reactors are concentrated and be placed in muffle furnace react 5.5h at 850 ℃, reacted rear cooling described a plurality of independent vacuum sealed reactors;
(5) the described a plurality of independent vacuum sealed reactor that fractures under vacuum condition, reactor bottom puts gas the purifying gained gas that Dewar container for liquefied nitrogen bottle absorption reaction generates; And
(6) gained gas is entered to two-way sample introduction gas isotope mass spectrometer and carry out oxygen isotope analysis.
The present invention is not traditional offline mode, but adopt the corresponding reactor of a sample, after these reactors are vacuumized to processing, according to independent tube sealing principle, make respectively a plurality of independent vacuum sealed reactors, then these a plurality of independent vacuum sealed reactors are concentrated to be placed in muffle furnace and react, therefore, the method according to this invention not only can avoid due to sample, being placed in prior art the shortcoming of the oxygen isotope memory effect causing in same fixed reactor, improve precision of analysis, also because sample is without reaction in order one by one, thereby can mass simultaneous analytic sample, improve sample analysis speed.
In addition, the method according to this invention, sulfate can react with graphite under low temperature (850 ℃), therefore, with respect to conventional carbon reducing process, at high temperature (more than 1100 ℃), react, further avoid the remarkable heat interchange occurring between gas that conventional carbon reducing process produces the in the situation that of high temperature and the reactor of heat, thereby further reduced memory effect.
Therefore, method of the present invention had both realized the accuracy of analyzing, and had improved again analysis speed, had realized the test fast continuously of oxygen isotope in a large amount of sulfate radicals.
Accompanying drawing explanation
Fig. 1 is according to the schematic diagram of the analytical equipment of oxygen isotope in sulfate radical of the present invention; And
Fig. 2 is according to the process flow diagram of the analytical approach of oxygen isotope in sulfate radical of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail, to make those skilled in the art can implement according to this with reference to instructions word.
As shown in Figure 1, according to the analytical equipment of oxygen isotope in sulfate radical of the present invention, comprise: a plurality of reactors, described reactor one end opening and other end sealing, for loading sample and the dag of containing sulfate radicals, and vacuum withdraw device, by a plurality of silicone tubes, be connected with the openend of described reactor, be used for vacuumizing processing, make described reactor form vacuum system, wherein this vacuum withdraw device comprises mechanical pump and diffusion pump 4, cold-trap 5 and vacuum manometer 8, cold-trap 5 one end connect mechanical pump and diffusion pump 4 by glass pipe 10, the other end connects vacuum manometer 8 by glass pipe 10, on glass pipe between mechanical pump and diffusion pump 4 and cold-trap 5, be provided with vacuum valve 7, on glass pipe between vacuum manometer 8 and each silicone tube, be respectively arranged with vacuum valve 3.
With reference to figure 2, the barium sulphate of usining is originated as sulfate radical as example, but is not limited to this, and sulfate radical also can come from calcium sulphate, illustrates according to the analytical approach of oxygen isotope in sulfate radical of the present invention, comprises the following steps:
(1) barium sulphate and dag being take to the ratio (30mg barium sulphate sample, 60mg dag) that weight ratio is 1: 2 is uniformly mixed, barium sulphate sample and dag are fully mixed, then, potpourri is packed in quartz ampoule 1, repeatedly abovementioned steps, prepares a plurality of quartz ampoules 1 that barium sulphate and dag are housed.
(2) described a plurality of quartz ampoules 1 are connected to the glass pipe 10 of vacuum withdraw device by a plurality of silicone tubes 2, valve-off 3, then open mechanical pump and diffusion pump 4, and on cold-trap 5, put liquid nitrogen cup 6, open successively valve 7 and valve 3, a plurality of quartz ampoules that barium sulphate sample and dag are housed are vacuumized to processing simultaneously.
(3) by the vacuum tightness of 8 pairs of vacuum systems of vacuum manometer, monitor, when vacuum manometer 8 monitors vacuum tightness and reaches 0.01Pa, use flame gun 9 respectively each quartz ampoule to be forged and taken off at the mouth of pipe 3-4cm place apart from quartz ampoule, form a plurality of independent vacuum sealed silica envelope reactors.
(4) a plurality of independent vacuum sealed silica envelopes of forging being taken off are concentrated and are placed in muffle furnace react 5.5h at 850 ℃, have reacted rear cooling described a plurality of independent vacuum sealed silica envelopes.
(5) the described a plurality of independent vacuum sealed silica envelope that fractures under vacuum state, quartz ampoule bottom puts Dewar container for liquefied nitrogen bottle and collects carbon dioxide the purifying gained carbon dioxide that reaction generates.
(6) gained carbon dioxide is entered to two-way sample introduction gas isotope mass spectrometer and carry out oxygen isotope analysis.
Numerical value with methods analyst international standards barium sulphate of the present invention (NBS-127) is as shown in table 1.
Table 1
As known from Table 1, during the isotope of method of the present invention oxygen in analyzing sulfate radical, that coincide with international standard is consistent, proves that method of the present invention is accurate and reliable.
The foregoing is only to explain embodiments of the invention; not attempt is done any pro forma restriction to the present invention according to this; therefore, all have under identical creation spirit, do relevant any modification of the present invention or change, all must be included in the category that the invention is intended to protection.
Claims (8)
1. an analytical approach for oxygen isotope in sulfate radical, is characterized in that, comprises the following steps:
(1) pack in reactor after sample and dag are uniformly mixed by predetermined ratio, repeatedly abovementioned steps, prepares a plurality of reactors that sample and dag are housed;
(2) described a plurality of reactors are connected to vacuum withdraw device to vacuumize processing;
(3) when the vacuum tightness of vacuum system reaches predetermined value, use flame gun to forge respectively and get described a plurality of reactor, form a plurality of independent vacuum sealed reactors;
(4) described a plurality of independent vacuum sealed reactors are concentrated under predetermined temperature and react the schedule time, reacted rear cooling described a plurality of independent vacuum sealed reactors;
(5) the described a plurality of independent vacuum sealed reactor that fractures under vacuum state, collects gas the collected gas of purifying that reaction generates; And
(6) gained gas is carried out on mass spectrometer to oxygen isotope analysis.
2. analytical approach according to claim 1, is characterized in that, in described step (1), this sample is barium sulphate or calcium sulphate.
3. analytical approach according to claim 2, is characterized in that, sample be take the ratio that weight ratio is 1: 2 and mixed with dag.
4. analytical approach according to claim 1, is characterized in that, in described step (2), described a plurality of reactors are connected to vacuum withdraw device by silicone tube.
5. analytical approach according to claim 1, is characterized in that, in described step (3), the vacuum tightness of this vacuum system is 0.01Pa.
6. analytical approach according to claim 1, is characterized in that, in described step (3), uses flame gun to forge and get at distance described reactor opening 3-4cm place.
7. analytical approach according to claim 1, is characterized in that, in described step (4), described temperature of reaction is 850 ℃, and the reaction time is 5.5h.
8. analytical approach according to claim 1, is characterized in that, in described step (5), at reactor bottom, puts the gas that Dewar container for liquefied nitrogen bottle absorption reaction generates.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110031536A (en) * | 2019-04-30 | 2019-07-19 | 核工业北京地质研究院 | Oxygen isotope composition analysis extraction element and method in a kind of rock and mineral |
| CN110143590A (en) * | 2019-06-06 | 2019-08-20 | 中国地质科学院水文地质环境地质研究所 | A kind of device and method that Zn/Fe flame sealed-tube method prepares graphite |
| CN111983007A (en) * | 2020-08-27 | 2020-11-24 | 上海化工研究院有限公司 | For determining nitric acid or nitrate15Method and apparatus for N isotope abundance |
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| US20090114809A1 (en) * | 2005-09-02 | 2009-05-07 | Australian Nuclear Science & Technology Organisation | Isotope ratio mass spectrometer and methods for determining isotope ratios |
| CN102156163A (en) * | 2010-08-03 | 2011-08-17 | 中国科学院地质与地球物理研究所 | Method for analyzing layered fluorination of diatom sample |
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| US20090114809A1 (en) * | 2005-09-02 | 2009-05-07 | Australian Nuclear Science & Technology Organisation | Isotope ratio mass spectrometer and methods for determining isotope ratios |
| CN102156163A (en) * | 2010-08-03 | 2011-08-17 | 中国科学院地质与地球物理研究所 | Method for analyzing layered fluorination of diatom sample |
Non-Patent Citations (2)
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| A. GLESEMANN 等: "On-Line Sulfur-Isotope Determination Using an Elemental Analyzer Coupled to a Mass Spectrometer", 《ANAL. CHEM.》 * |
| 万德芳 等: "碳还原法分析硫酸盐的氧同位素组成", 《矿床地质》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110031536A (en) * | 2019-04-30 | 2019-07-19 | 核工业北京地质研究院 | Oxygen isotope composition analysis extraction element and method in a kind of rock and mineral |
| CN110143590A (en) * | 2019-06-06 | 2019-08-20 | 中国地质科学院水文地质环境地质研究所 | A kind of device and method that Zn/Fe flame sealed-tube method prepares graphite |
| CN110143590B (en) * | 2019-06-06 | 2024-04-16 | 中国地质科学院水文地质环境地质研究所 | Device and method for preparing graphite by Zn/Fe flame tube sealing method |
| CN111983007A (en) * | 2020-08-27 | 2020-11-24 | 上海化工研究院有限公司 | For determining nitric acid or nitrate15Method and apparatus for N isotope abundance |
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Application publication date: 20140326 |