CN102759562B - Method for in-situ distillation and on-line measurement of Os in Carius tube - Google Patents
Method for in-situ distillation and on-line measurement of Os in Carius tube Download PDFInfo
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- CN102759562B CN102759562B CN201110112039.9A CN201110112039A CN102759562B CN 102759562 B CN102759562 B CN 102759562B CN 201110112039 A CN201110112039 A CN 201110112039A CN 102759562 B CN102759562 B CN 102759562B
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Abstract
The invention discloses a method for in-situ distillation and on-line measurement of Os in a Carius tube. The method comprises the following steps: a sample is decomposed by inverse aqua regia in a Carius tube method, the generated OsO4 steam enters into a carrier gas port of an atomizer under carry of Ar gas through a special interface, Ir solution is introduced into a liquid inlet of the atomizer, and mixed aerosol comprising Os and Ir is formed at a nozzle of the atomizer. According to the invention, in comparison with the prior art, the Ar gas enters into the carrier gas port of the atomizer along with the Os steam and reaches a rectangular pipe, and the Ir standard solution introduced from the liquid inlet pipe is used for on-line discrimination and correction, so that the measuring precision is improved; after the sample is dissolved by the Carius tube, the in-situ distillation is directly carried out without separation, and meanwhile, a ratio and a content of an Os isotope can be obtained by on-line precise measurement. In comparison with the original on-line measurement method, the method, provided by the invention, is difficult to put out a fire, and in comparison with a solution feeding measurement method, a memory effect is remarkably reduced.
Description
Technical field
The present invention relates to fixed year of a kind of Os and isotope tracer technique, relate to particularly a kind of Carius pipe original position distillation Os On-line Measuring Method.
Background technology
In recent years, Re-Os (rhenium-osmium) is subject to paying attention to more and more widely with isotope tracer technique for fixed year, molybdenite is one of important application approach of Re-Os isotopic system in fixed year, from the beginning of the eighties in last century, rising the fixed year method of existing a lot of molybdenites and correlative study so far reports (as [R.Markey, H.Stein and J.Morgan, Talanta, 1998, 45, 935-946], [Andao Du, Shuqi Wu, Dezhong Sun Wang, W.Qu, R.Markey, H.Stein, J.Morgan and D.Malinovsky, Preparation and Certification of Re-Os Dating Reference Materials:Molybdenite HLP and JDC, Geostandard and Geoanalytical Research, 2004, 28 (1): 41-52], [Standarizing Re-Os geochronology:A new molybdenite Reference Material (Henderson, USA) and the stoichiometry of Os salts, Chem.Geol.244 (2007) 74-87], [Holly Stein, Anders Schersten, Judith Hannah and Richard Markey, Subgrain-scale decoupleing of Re and 187Os and assessment of Laser ablation ICP-MS spot dating in molybdenite, Geoc.Cosmo.Acta 67 (19) 2003 3673-3686], [Dmitry Malinovsky, Ilia Rodushkin, Douglas Baxter, Bjorn Ohlander, Simplified method for the Re-OS dating of molydenite using acid digestion and isotope dilution ICP-MS, Anal.Chem.Acta, 463 (2002) 111-124], [W.J.Qu, A.D.Du, D.M.Zhao.Talanta.2001, 55, 815-820], [Qu Wenjun, Du Andao, the molten sample inductivity coupled plasma mass spectrometry of high-temperature closed Accurate Determining molybdenite rhenium-osmium geological age, the test of rock ore deposit, 2003, 22 (4): 254-262)], [Qu Wenjun, Du Andao, appoint quiet, 2008, analytical chemistry, hydrogen peroxide is the impact on rhenium-osmium signal intensity and age in pyritous molten sample process, 36 (2) 223-226].The discovery of increasing new molybdenum deposit, causes the fixed year method research of Re-Os of a new round and improves upsurge.Existing method is used negative ion thermal ionization mass spectrometry (tims) (N-TIMS) determination techniques mostly, the feature of this technology is the high [H.J.Stein of precision, R.J.Markey, J.W.Morgan, A.Du and Y.Sun, Econ.Geol., 1997, 92, 827-835], [D.Selby and R.A.Creaser, Econ.Geol., 2001, 96, 197-204], [Du Andao, Zhao Dunmin, Wang Shuxian, Sun Dezhong, Liu Dunyi, 2001, Carius manages molten sample-negative ion hot surface MALDI-MS Accurate Determining Re-Os isotopic geological age, the test of rock ore deposit, 20 (4) 247-252], but operating cost is also high, and the determinand of the purity of having relatively high expectations is to guarantee higher emission efficiency and high sensitivity, thereby make analysis process longer.Although ICP-MS method precision is slightly poor compared with N-TIMS, analysis efficiency is high, pre-treatment flow process is relatively simple.But conventionally still need to before Os measures, carry out separation, distillation and two kinds of methods of extraction are generally taked in the separation of Os.Some N-TIMS method is still needed and is wanted further micro-distillation.The conventional way of distillation needs Reusability cucurbit and the larger relevant auxiliary equipment of volume, not only takies larger space, and it cleans the time that often needs to have more than experiment several times, needs to consume the reagent such as a large amount of acid, alkali amplification quantity waste liquid side by side simultaneously.Plug-in type (Plug in) bottle Os distillation technique can overcome the problems referred to above, but bottle used more easily adsorbs Os.Extraction separation method, the reextraction process of conventionally still needing, needs the time of cost longer.[Liang Qi, Mei-Fu Zhou, Jianfeng Gao et al, 2010, An improved Carius tube technique for determination of low concentrations of Re and Os in pyrites.JAAS, 25, 585-589.] and [Li Chao, Qu Wenjun etc., Carius pipe is the research of the quick separated osmium method of distillation directly, 2010, the test of rock ore deposit, 29, 14-16] etc. successively reported the method that adopts original position separated Os, shortened flow process, improved work efficiency, but still needing first Os to be carried out to separation then measures again.
[Deborah R.Hassler, Bernhard Peucker-Ehrenbrink, Greg E.Ravizza, Rapid determination of Os isotopic composition by sparging OsO
4into a magnetic-sector ICP-MS, Chem.Geol., 2000,166,1-14] etc. be by OsO
4directly link the isotopics of spraying (Sparging) method on-line determination Os for quarter bend, but acid vapor in contrary chloroazotic acid is stronger to quarter bend corrosion, quarter bend inwall and the mouth of pipe easily deposit sour insoluble rufous dirt.In addition, must disconnect being connected of quarter bend and interface owing to changing sample, thin mouthful of end inner tube of quarter bend is direct exposed in air, even if in time by carrier gas flux set to zero, is also easy to cause plasmatorch flame to extinguish.Meanwhile, OsO
4steam is directly introduced quarter bend, cannot introduce solution, before therefore, adding thermal distillation at Os, measuring and to start, can not carry out the adjustment of instrument optimization and mass calibration.
Summary of the invention
The object of the present invention is to provide a kind of Carius pipe original position distillation Os On-line Measuring Method, to improve the defect existing on known technology.
For achieving the above object, Carius pipe original position distillation Os On-line Measuring Method provided by the invention, is by OsO
4steam is connected to the carrier gas port of atomizer rather than directly links quarter bend, compares atomizer inlet as usual introduce solution with the method for Hassler, is convenient to the adjustment of instrument optimization, with the mass fractionation correction that common Ir standard solution carries out Os, has improved measuring accuracy.The present invention only needs an original position distillation to simplify [R.Schoenberg, T.F.
j.D.Kramers, International Journal of Mass Spectrometry, 2000,197,85-94] the second distillation flow process of report.The original position Os isotopic ratio that distilled online Accurate Measurement after Carius manages molten sample, makes in previous work the easily problem of fire extinguishing be improved, ON-LINE SEPARATION 20 minutes, and this method has more practicality.Newly-designed web member is very little glassware, is easy to clean.Comparing memory effect with solution sample introduction assay method obviously reduces.
In detail, Carius pipe original position distillation Os On-line Measuring Method provided by the invention, its step comprises:
The contrary chloroazotic acid of Carius pipe decomposes the OsO producing after sample
4steam enters the carrier gas port of atomizer under the carrier band of Ar gas by web member of the present invention, the inlet of atomizer is introduced Ir solution, the nozzle place of atomizer forms the combination gas colloidal sol containing Os and Ir, proofreaies and correct the mass fractionation of Os isotopic ratio with real-time Ir isotopic ratio.
Described On-line Measuring Method, wherein, Carius pipe is placed in and temperature is housed for can produce OsO
4in the PAF bottle of the boiling water of steam.
Described On-line Measuring Method, wherein, the weight concentration of Ir solution is 5-10ng/ml, solution medium is the HNO of volume ratio 1-3%
3.
The present invention and known technology difference, be after Os steam enters atomizer carrier gas port and arrive quarter bend with Ar gas carrier band, and the present invention is difficult for fire extinguishing, and memory effect weakens.Common Ir standard solution is introduced for discriminating against and proofread and correct in line mass from inlet, and measuring accuracy is improved.Carius manages after molten sample, without separation, and can direct in-situ distillation simultaneously online Accurate Measurement Os isotopic ratio and content.Web member is glassware, cheap, and volume is little, and easy to clean has been saved time and the reagent of a large amount of cleaning bodies.
Accompanying drawing explanation
Fig. 1 a is web member schematic diagram of the present invention; Fig. 1 b is connected with schematic diagram capillaceous for this web member.
Fig. 2 is the schematic diagram that web member of the present invention is connected with Ar gas sample feeding pipe, Carius pipe, PAF bottle and atomizer carrier gas port respectively.
Fig. 3 is detecting device dead time in the embodiment of the present invention.
Fig. 4 is that the embodiment of the present invention is with the measurement data of 0.010g molybdenite standard specimen JDC (national standard material GBW04436).Fig. 4 a be signal intensity with the change curve of distillation time, Fig. 4 b is that isotopic ratio is with the situation of change of distillation time.
Fig. 5 is the disparity map of distillation speed under the embodiment of the present invention three kinds of distillation modes of being drawn by measured data.
Fig. 6 is the distillation curve trend measured drawing of three kinds of distillation modes of different samples in the embodiment of the present invention.
Embodiment
The present invention links the gas outlet of Carius pipe the carrier gas port of atomizer, introduces Ir standard solution and can carry out easily online mass fractionation correction, and play the effect of monitoring instrument optimum condition.The OsO producing
4steam arrives rapidly atomizer under the carrier band of a large amount of carrier gas (Ar), is evenly distributed on Ir solution (the medium 3%HNO by the inlet lifting of atomizer
3) in the aerosol that produces, and together enter quarter bend with these tiny uniform gasoloids.
Ir standard solution is for discriminating against and proofread and correct in line mass, and measuring accuracy is improved.Carius manages after molten sample, without separation, and can direct in-situ distillation simultaneously online Accurate Measurement Os isotopic ratio and content.
Below in conjunction with drawings and Examples, technical scheme of the present invention is further described.
In On-line Measuring Method of the present invention, also needing has the web member that can be connected with Ar gas draft tube, Carius pipe and atomizer carrier gas port respectively, as shown in Figure 1a, web member 10 its integral body in Fig. 1 a are a glass tube to the structure of this web member, and the upper end of this glass tube is carrier gas air intake opening 11; In this glass tube, be the inside and outside two-layer pipe of concentric, its inner tube is carrier gas passage 13, and its outer tube is OsO
4steam and carrier gas combination gas arrive the mixed gas passage 14 of atomizer 12.The inner wall sealing of one end of this carrier gas passage 13 and carrier gas air intake opening 11 connects as one, to avoid carrier gas to leak and to avoid OsO
4the mixed gas of steam and carrier gas enters carrier gas passage 13.The other end of carrier gas passage 13 connects kapillary 15 (as shown in Figure 1 b).One side of mixed gas passage 14 offers the interface 16 of the carrier gas port A (this atomizer is known technology, does not represent in detail in figure) of a connection atomizer.
Fig. 2 is the annexation of web member of the present invention when concrete use.Carius pipe 20 is placed in the 250ml PFA bottle 21 that water is housed, the water being heated in PAF bottles by the adjustable electric heating cover 22 of temperature.The gas outlet 23 of Carius pipe 20 is tightly connected with one end of the mixed gas passage 14 of web member, and the carrier gas passage 13 of this web member connects kapillary 15 and inserts in Carius pipe 20.The interface 16 that mixed gas passage 14 1 sides of web member are offered is connected to the carrier gas port A that connects atomizer, and Ir standard solution 24 is connected to the inlet B of atomizer.For the sealing that guarantees each junction with avoid the emulsion tube because air-flow is connected use when excessive by each to wash open, at the place, gas outlet of Carius pipe, carrier gas Ar tracheae is connected Carius pipe place and mixed gas passage interface with glass tube junction, glass tube, be provided with a bulge 201,101,111 and 141 respectively.
Refer to Fig. 2, carrier gas air-flow C enters in Carius pipe 20 through carrier gas passage 13 and the kapillary 15 of web member, and Carius manages the OsO of 20 interior generations
4steam (representing with sweep in Fig. 2) arrives rapidly the nozzle of atomizer by mixed gas passage 14 under the carrier band of carrier gas, is evenly distributed on Ir solution (the medium 3%HNO by the inlet B lifting of atomizer
3) in the aerosol that produces, and together enter quarter bend with these tiny uniform gasoloids.
Below that web member of the present invention is for the concrete operations flow process of On-line Measuring Method.It should be noted that, the present invention in the following description, is not explained in detail the known content of this area etc., all cognitive because these terms are those skilled in the art.
Accurately take the standard substances such as HLP or JDC in Carius, add appropriate Re-Os mixed diluent and sub-boiling distillation HCl, HNO
3sample dissolution.Solvent freezing Carius pipe is opened, after being placed on before distillation and rising again in ice-water bath, with ultrapure water, one times of Sample Dilution is measured afterwards.Preprepared interface and kapillary combination are used in to H
2o
2the silicone tube soaking in water is enclosed within the venturi portion of Carius pipe, by shown in Fig. 2, assembles, and with Ir solution, adjusts carrier gas size, before starting to measure, the Carius pipe connecting is placed in to the PFA bottle that micro-boiling water is housed.Adjusting sample gas starts online distillation measurement to Ir signal stabilization, does quality discrimination proofread and correct with Ir.The separation of Re adopts acetone extract method.
The present invention hangs the globule for preventing the excessive Carius of the causing pipe of bubble top, can guarantee the demand of solution atomization again simultaneously, keeps gross sample gas within the scope of 0.7-0.9L/min.If the caliber of kapillary 15 is excessive, shut the bottom that kapillary can be inserted in to Carius pipe one end, and with pin, wear successively from different directions some apertures along kapillary from top to bottom, make carrier gas by progressively shunting (as the amplifier section that circle in Fig. 2 represents, arrow wherein represented downwards, and to the right three directions) left.Be usually in liquid level bottom, to prick 4 of 0.2mm apertures, tubule more than liquid level is partly pricked 6 of 0.2mm apertures, 4 of 0.3mm apertures, can guarantee to observe tiny and uniform bubble bloats from solution.
Detecting device coincidence correction
In isotopic ratio is analyzed, in order to obtain good preci-sion and accuracy, must proofread and correct the dead time, particularly count sufficiently high time.Coincidence correction formula is:
C
corr＝C
obs/(1-C
obs*τ)
In formula, C
corrfor the isotope count value after coincidence correction; C
obsthe isotope count value observing while being set as zero for the instrument dead time; τ is the detecting device dead time.Its key step referring to, the serial solution of preparation is measured when the dead time is set as zero
185re and
187re counting, the ratio to each concentration point of measuring
187re/
185re respectively by 0,10,20,30,40,50,60,70ns carries out coincidence correction, with the ratio of common Re
187re/
185re=1.6740 is normalized, and normalized ratio is to proofreading and correct dead time mapping used, and the time corresponding to joining of each concentration straight line is needs definite dead time.The present embodiment dead time result is 28ns.The mensuration in dead time still has error, and the thinning agent adding preferably makes to record ratio in 0.5-1.0 scope, further to reduce the impact of dead time measuring error correlative value Accurate Measurement.Figure 3 shows that the curve map of the present embodiment detecting device dead time.
Mass fractionation correction
The Ir introducing in order to solution spray form carries out on-line correction to the mass fractionation of Os isotopic ratio; Re is used through the Re isotopic ratio standard of accurate calibration and carries out outside insertion correction.Conventionally, use
190os does single thinning agent molybdenite sample analysis of thinning agent, owing to not having suitable Os isotopic ratio for measuring, to be difficult to carry out online mass fractionation correction.Therefore, although usually relating to a very little unknown quality, discriminates against molybdenite sample analysis, for ratio
187os/
190os, its quality is discriminated against nearly ppt.In recent years, molybdenite sample N-TIMES age determination precision has reached suitable with it level.Therefore, quality discrimination is proofreaied and correct and is seemed extremely important.Quality discriminates against to proofread and correct has following several method available.A kind of method is to make thinning agent with common Os.But, in common Os, contain considerable
187os must pay attention in isotopic dilution calculates.In molybdenite and blank, all may contain a small amount of common Os, this makes situation become complicated; With common Os, make thinning agent, just can not monitor the existence of common Os in sample, and in sample, the existence of any common Os all will cause mixing the significant change of rear Os diluent ratio.When analyzing the sample of a small amount of sample (< 10mg) or relatively young sample and low Re content, it is most important that common Os and/or blank may become.In addition, with common Os, make the sample that thinning agent is obviously not suitable for those low contents, high radioactivity (LLHR) because, content low wherein the amount of common Os can not ignore and,
187the concentration of Os is significantly higher than other Os isotopes.Therefore, although lack quality, discriminate against correction, some authors still advise using
190the thinning agent that Os analyzes as molybdenite.Another method is that outside insertion is proofreaied and correct, and before and after sample analysis, all carries out the standard specimen of known ratios and measures, then proofread and correct with linear interpolation.This method is in most cases feasible, and method is applicable to the mensuration of Re very much, still, is not very applicable to the mensuration of Os, because the memory effect of Os is strong, causes scavenging period long, has a strong impact on measuring speed.
In order to realize original position distillation and on-line determination, the present invention is except having carried out improvement, simultaneously by the Ir standard solution monitoring instrument condition of 10ng/ml and proofreaied and correct the mass fractionation of Os to sampling device.Correction coefficient is real-time instrument quality fractionation factor between element.Concrete grammar is: measure the isotopic ratio of element to be measured (Os) and doped chemical (Ir) simultaneously, and suppose that the quality discrimination of two kinds of elements is consistent.Quality is discriminated against general useable linear function, power function, exponential function description.Reference literature of the present invention [Y.Sun, P.Xu, J.Li, K.He, Z.Chu and C.Y.Wang, Anal.Methods, 2010,10,1039-1047] and [K.Suzuki, M.Feely and C.Reilly, Geochim.J., 2001,35,29-35] report, with linear law, proofread and correct: take respectively 3.75ng, the common Os of 7.5ng and 15ng also processes by unknown sample, records
188os,
189os,
190os and
192os couple
190the ratio of Os (Rm) and ratio
191ir/
193ir and
193ir/
191ir, with theoretical ratio R t and record ratio R m calculated mass fractionation factor F (F=Rm/Rt), the fractionation factor F obtaining can obtain linear equation Y=aX+b to corresponding of poor quality recurrence.With the linearly dependent coefficient that front 4 recurrence obtain, be 0.9972; By the related coefficient that all 6 recurrence obtain, be 0.9969, the two does not have marked difference.Therefore, by the ratio recording (
191ir/
193ir) m and theoretical value (
191ir/
193ir) t can calculate (
187os/
190os) m/ (
187os/
190os) t and (
192os/
190os) m/ (
192os/
190os) t.Actual measurement data shows there is no significant difference by the result that linear law and law of exponent obtain, and therefore, the present invention selects fairly simple linear law correction mass fractionation.
When actual sample is measured, only need to survey 8 points (approximately 16 minutes), get at the 2nd～7 and carry out statistical computation, the distillation curve of acquisition is shown in Fig. 4, is 0.010g molybdenite standard specimen JDC measurement data, and every point measurement time is 2 minutes.Ratio
191ir/
193ir,
187os/
190os and
192os/
190the RSD of Os is respectively 0.17%, 0.12%, and 0.50%.
For obtaining high-precision measurement data, the present invention had once carried out measuring under three kinds of distillation modes the comparison of effect:
1) Ar gas enters the solution bottom (bubble is excessive, the Carius inside pipe wall globule easy to hang) in Carius pipe completely.
2) part Ar gas enters the solution bottom in Carius pipe, and remainder directly switches to atomizer (connected mode is more complicated, and effect is better) with threeway before entering Carius pipe;
3) it is inner that Ar gas enters Carius pipe completely, but only have small part to enter into the solution bottom in pipe, and major part enters space (connecting simple, effective) more than solution in Carius pipe along pin hole.
What Fig. 5 drew is the normalization comparison diagram of three kinds of mode distillation curves, with three isotopic average counters of unit concentration in specific sample, compares, and horizontal ordinate is online distillation time.Fig. 5 has shown the difference of three kinds of distillation mode distillation speeds.Fig. 6 is the integrated form of Fig. 5 curve, shows the distillation trend of three kinds of distillation modes of different samples.When distillation mode is identical, the distillation trend of different samples is close, as 1HLP and 1JDC is close, 3HLP is close with 3JDC.The distillation trend of the different distillation modes of same sample is compared, can find out that the counting that the first distillation mode obtains than the 3rd distillation kind mode is high, if 1HLP is higher than 3HLP; 1JDC is higher than 3JDC.But, while distilling due to the former bubble too large, cause a large amount of globules to hang over Carius inside pipe wall, affect measuring accuracy, consider that the second distillation mode connects some complexity simultaneously, therefore the present invention has selected the third mode, and which still-process relaxes steadily, can obtain many group intensity enough large stable data for statistical computation, therefore, precision is better.
On Fig. 6, each right-angled intersection point has marked 90% required time that response curve reaches total mark intensity, and 1,2,3 three kind of mode be respectively 10 minutes, 16 and 20 minutes.
About memory effect problem, in the present invention, Carius pipe, emulsion tube and Teflon pipe etc. are all disposable uses, and the impact of memory effect obviously weakens, and uses 30%H
2o
2and 3%HNO
3alternately clean, only need 8 minutes each isotope countings of Os can be down to blank level.Experiment shows, measures after same sample, with conventional soln sampling system, cleans to same count level, at least needs to spend more 5 minutes.
The measurement result of standard substance HLP and JDC
The present invention to standard substance HLP (GBW04435) and JDC (GBW04436) repeatedly measurement result be listed in the table below 1, it is consistent in range of uncertainty with recommendation 221.4 ± 5.6Ma and 139.6 ± 3.8Ma with 139.9 ± 0.48Ma that mean value is respectively 221.4 ± 0.8Ma.
Up to now, standard substance HLP and JDC in the world a plurality of laboratories are widely used, the different instruments such as each use for laboratory ICP-MS, N-TIMS or diverse ways have been measured respectively the age of above-mentioned standard specimen, table 2 has been listed the correlated results of publishing, the separation etc. that comprises bearing calibration, the measuring method of Os that quality is discriminated against and whether need to carry out in advance Os.Quality is discriminated against bearing calibration and is comprised: (i) in line mass, discriminate against and proofread and correct, (ii) common Os correction method; (iii) outside insertion correction method; (iv) two thinning agent isotope dilution method.Measuring method comprises: (i) original position distillation on-line determination is measured with (ii) in advance separated rear solution atomization method.Be combined with Ir and discriminate against alignment technique in line mass, the present invention distills On-line Measuring Method by original position, and gained molybdenite standard specimen age result is one of 2 kinds of methods of relative standard deviation minimum in all ICP-MS methods.The RSD value of the age result of HLP and JDC is respectively 0.38% and 0.44%.The internal accuracy at HLP age of the present invention almost can compare favourably with high precision N-TIMS result [as the result of Selby et al and Markey et al], although the uncertainty at N-TIMS method gained age (2 σ) is far below ICP-MS method, but it should be noted that, all N-TIMS methods all adopt 0.31% uncertainty as Re disintegration constant, and all ICP-MS methods have all adopted 1.02%.
Of common Os, make the mass fractionation correction of Os, owing to being correction between the different isotopes of identical element, therefore, conventionally can obtain good effect.Although mass fractionation of the present invention is to proofread and correct between different element Os and Ir, from the RSD data of table 2, calibration result or satisfied.This may be mass number and the ionization potential (8.7 of Os and Ir; 9.0eV) very approaching result all, this bearing calibration can be more favourable to the sample that contains a small amount of common Os.Although the internal accuracy that outside insertion obtains is better,, in order to reduce the impact of Os memory effect, the method is had to spend the longer time and is cleaned thoroughly.Two thinning agent methods should be optimal in four kinds of bearing calibrations discussed here, yet, due to multifactorial impacts such as its longer flow process and the preparation of two thinning agent and calibrations, might not obtain desirable result.
The measurement result of table 1: standard substance HLP (～8mg) and JDC (～100mg)
Table 2
Claims (3)
1. Carius pipe original position is distilled an Os On-line Measuring Method, and its step comprises:
Carius pipe method is decomposed after sample against chloroazotic acid, by web member by OsO
4steam is introduced the carrier gas port of atomizer; Web member integral body is a glass tube, and upper end is carrier gas air intake opening; In glass tube, be the inside and outside two-layer pipe of concentric, its inner tube is carrier gas passage, and outer tube is OsO
4steam and carrier gas arrive the mixed gas passage of atomizer; The inner wall sealing of one end of this carrier gas passage and carrier gas air intake opening connects as one, to avoid carrier gas to leak and to avoid OsO
4the mixed gas of steam and carrier gas enters carrier gas passage; The other end of carrier gas passage connects kapillary; One side of mixed gas passage offers the interface of the carrier gas port of a connection atomizer; One end of the gas outlet of Carius pipe and the mixed gas passage of web member is tightly connected, and the carrier gas passage of this web member connects kapillary and inserts in Carius pipe; The interface that mixed gas passage one side of web member is offered is connected to the carrier gas port that connects atomizer; OsO
4steam enters the carrier gas port of atomizer under the carrier band of Ar gas, and the inlet of atomizer is introduced Ir solution, and the nozzle place of atomizer forms the combination gas colloidal sol containing Os and Ir.
2. On-line Measuring Method according to claim 1, wherein, Carius pipe is placed in and temperature is housed for can produce OsO
4in the PAF bottle of the boiling water of steam.
3. On-line Measuring Method according to claim 1, wherein, the weight concentration of Ir solution is 5-10ng/ml, solution medium is the HNO of volume ratio 1-3%
3.
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| CN106442698A (en) * | 2016-11-21 | 2017-02-22 | 南京大学 | Re-Os isotope analysis method for oil and gas system organic matter research |
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| CN110146583B (en) * | 2019-04-26 | 2020-08-11 | 中国科学院地质与地球物理研究所 | Method for decomposing sample by Carius tube and method for analyzing isotope of Re-Os |
| CN111876597B (en) * | 2020-08-03 | 2022-02-22 | 国家地质实验测试中心 | Extraction of radioactive cause from molybdenite187Methods for Os |
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|---|---|---|---|---|
| CN1030799C (en) * | 1992-10-10 | 1996-01-24 | 中国有色金属工业总公司昆明贵金属研究所 | Method for measuring high OS and Ru contents in complex solution |
| CN101113968A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for on-line measuring drug-making chemicals with ion transfer spectrometer |
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2011
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