CN106769346A - The method of hydrogen isotope in analysis water - Google Patents
The method of hydrogen isotope in analysis water Download PDFInfo
- Publication number
- CN106769346A CN106769346A CN201710168894.9A CN201710168894A CN106769346A CN 106769346 A CN106769346 A CN 106769346A CN 201710168894 A CN201710168894 A CN 201710168894A CN 106769346 A CN106769346 A CN 106769346A
- Authority
- CN
- China
- Prior art keywords
- collecting pipe
- hydrogen
- vacuum
- water sample
- water
- 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.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The present invention relates to isotope analysis technical field, a kind of method for analyzing hydrogen isotope in water is disclosed, the described method comprises the following steps：I () will be collected after the two ends of the capillary of water sample are sealed and be put into the first collecting pipe；(ii) after being put into the first collecting pipe in step (i) the second collecting pipe (10) equipped with chromium powder and carry out vacuumize process, the second collecting pipe (10) is sealed；(iii) make the capillary break-up in the first collecting pipe, under conditions of heating, the chromium powder in the second collecting pipe (10) is reacted with the water sample in capillary；(iv) treat that the chromium powder in step (iii) terminates with water sample reaction, second collecting pipe (10) is put into the 3rd collecting pipe, the 3rd collecting pipe is connected with analytical equipment afterwards, the hydrogen in the second collecting pipe (10) is discharged, hydrogen isotope analysis is carried out and is obtained hydrogen isotope ratio in water.The method that the present invention is provided has the advantages that high precision and reproducible.
Description
Technical field
The present invention relates to Stable Isotopic Analysis technical field, and in particular to a kind of method of hydrogen isotope in analysis water.
Background technology
With the development of isotope analysis technology, the modern times that the Stable Isotopic Analysis of water are increasingly becoming hydroscience field grind
Study carefully one of method.The stable isotope composition of water is considered as " fingerprint " of water, dynamic in analysis moisture source, migration and mixing etc.
The effect for becoming more and more important is played in the research of state process.Particularly D and18O, is considered as in the water-rock interaction without high temperature and strong
It is stable under strong evaporation conditionses, is the optimal environmental isotopes of spike Hydrodynamic Process.
The hydrogen isotope analysis method of water, domestic and international isotopic laboratory is generally used using some active metals unit
Element makees reducing agent, converts water into the metal method of hydrogen：Metal+water=metal oxide+hydrogen, then will react the hydrogen for producing
Gas carries out isotope analysis with gas isotope mass spectrograph.At present, in various countries' isotopic laboratory using it is more be metallic zinc
With uranium method.
Metal zinc reduction is set up by Friedman first, and its analysis method mainly has：(1) flow method, with two cold-traps
Make water sample in vapour form by the zinc stove at 400 DEG C, then the hydrogen charcoal absorption of generation is collected in gas sample pipe
Make mass spectral analysis.(2) band whether there is the reaction tube method of fat high vacuum stopcock, and water sample and zinc are directly loadable into, it is degassed after at 450 DEG C
Lower reaction, the hydrogen of generation can be introduced directly into spectrometer analysis.But because zinc metal active is poor, cause metal zinc reduction
Repeated bad, precision is not high enough, analyze data is not accurate enough.Craig establishes uranium reducing process, although the reaction of uranium reducing process
Speed is fast, precision is higher, analyze data is accurate, but metallic uranium radiation properties and the Radwastes treatment of generation in experiment
Influenceed Deng all being produced on work and ecological environment.
The content of the invention
The invention aims to the micro water sample of analysis that the hydrogen isotope analysis method and technology for overcoming existing water is present
Because sample is few, signal is weak during middle hydrogen isotope, the repeated bad of hydrogen isotope ratio, precision are inadequate in causing analysis water
High, analyze data is not accurate enough, and environment it is unfriendly the problems such as, there is provided the method for hydrogen isotope, the party in a kind of analysis water
Method has the advantages that reaction speed is fast, amount of samples is few, precision is higher, analyze data is accurate, reproducible, environment is friendly, and
And the method is simple to operate, using the means of independent encapsulation, multiple samples, more traditional off-line analysis can be simultaneously prepared
Detection method it is operational stronger, analysis efficiency is higher.
To achieve these goals, the present invention provide it is a kind of analyze water in hydrogen isotope method, methods described include with
Lower step：
I () will be collected after the two ends of the capillary of water sample are sealed and be put into the first collecting pipe；
(ii) by the first collecting pipe in step (i) be put into the second collecting pipe equipped with chromium powder and carry out vacuumize process it
Afterwards, the second collecting pipe is sealed；
(iii) make the capillary break-up in the first collecting pipe, under conditions of heating, make the chromium in the second collecting pipe (10)
Powder reacts with the water sample in capillary；
(iv) treat that the chromium powder in step (iii) terminates with water sample reaction, the second collecting pipe is put into the 3rd collecting pipe, afterwards
3rd collecting pipe is connected with analytical equipment, the hydrogen in the second collecting pipe of release carries out hydrogen isotope analysis and obtains hydrogen in water
Isotopic ratio.
By above-mentioned technical proposal, can quickly and efficiently analyze hydrogen isotope in water, during analysis reaction speed it is fast,
Amount of samples is few, high precision, analysis result are accurate, reproducible, and the method is simple to operate, environment is friendly, uses
Individually the means of encapsulation, can simultaneously prepare multiple samples, more traditional off-line analysis detection method it is operational stronger, analysis is imitated
Rate is higher.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the structural representation of pre-treatment platform；
Fig. 2 is the structural representation of the second collecting pipe.
Description of reference numerals
1st, vacuum line interface 2, vacuum communicating pipeline 3, pressure gauge
4th, the first cold-trap 5, the second cold-trap 6, absorption tube
7th, vacuum meter 8, vavuum pump 9, two-way piston
10th, the second collecting pipe 11, liquefied gas firelock 12, extension diameter section
13rd, dip section
Specific embodiment
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
One or more can be obtained with combination with one another between the endpoint value of individual scope and single point value, and individually between point value
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of method for analyzing hydrogen isotope in water, the described method comprises the following steps：
I () will be collected after the two ends of the capillary of water sample are sealed and be put into the first collecting pipe；
(ii) the first collecting pipe in step (i) is put into the second collecting pipe 10 equipped with chromium powder and carries out vacuumize process
Afterwards, the second collecting pipe 10 is sealed；
(iii) make the capillary break-up in the first collecting pipe, under conditions of heating, make the chromium powder in the second collecting pipe 10
Reacted with the water sample in capillary；
(iv) treat that the chromium powder in step (iii) terminates with water sample reaction, the second collecting pipe 10 is put into the 3rd collecting pipe, it
The 3rd collecting pipe is connected with analytical equipment afterwards, the hydrogen in the second collecting pipe 10 of release carries out hydrogen isotope analysis and obtains water
Middle hydrogen isotope ratio δ D.
According to the present invention, for the ease of the water sample of encapsulation collection, and in order to be beneficial to the outflow of water sample in subsequent operation with
Chromium powder reacts, and the capillary of the collection water sample can be quartz glass capillary；The size of the capillary is without especially
Limit, can be prepared by conventional glazier's drawing process, such as the length of described capillary can be 5-8cm, interior
Footpath can be 1-2mm.
According to the present invention, the acquisition method of the water sample can be to be injected into capillary by micro syringe, described
Water sample needs what can continuously be flowed when ensureing that water sample is in capillary in collection, and without tomography.
According to the present invention, in order to prevent it is described be collected the capillary attraction of water sample to chamber wall, be unfavorable for subsequently needs
Ruptured during release water sample, preferably use the first collecting pipe and receive the capillary, then place into the second collection equipped with chromium powder
Pipe, carries out subsequent operation.The material of first collecting pipe is not particularly limited, for example, can be quartz selection pipe.It is described
The shape and size of the first collecting pipe are not particularly limited, as long as the capillary can be accommodated, such as described first
Collecting pipe can be the collecting pipe of flat mouth round bottom, and length can be 4-5cm, and internal diameter can be 5-6mm.
According to the present invention, the operating process of the sealing is not particularly limited, and can be the conventional way in this area, example
Such as, it is possible to use liquefied gas firelock is heated to the collecting pipe of glass or quartz material, its melting sealing is made.It is molten for capillary
Envelope, sealing operation is collected water sample to treat it, and ensure water sample in the capillary continuous flowing and without tomography after, to its two
End is sealed；For the sealing of the second collecting pipe 10, because its bottom is enclosed construction, and the second collecting pipe 10 is carried out
During vacuumize process, its top is connected with the vacuum line interface 1 of pre-treatment platform, therefore, sealing operation is to use liquefied gas fire
Below junction of the rifle to the second collecting pipe 10 with the vacuum line interface 1 of pre-treatment platform, it is put into inside the second collecting pipe 10
The position more than openend of the first collecting pipe is heated, and the second collecting pipe 10 is fused and is sealed.
According to the present invention, the water sample needs to carry out vacuumizing place to containing its collecting pipe before being reacted with the chromium powder
Reason, in this manner it is ensured that the hydrogen that the hydrogen sample of final analysis is produced all from the water sample with chromium powder reaction,
So as to ensure the water sample for the hydrogen isotope analyzed all from collection.
According to the present invention, the vacuumize process of step (ii) is processed using pre-treatment platform, as shown in figure 1, before described
Treatment bench includes：It is vacuum line interface 1, vacuum communicating pipeline 2, pressure gauge 3, the first cold-trap 4, the second cold-trap 5, absorption tube 6, true
Sky meter 7, vavuum pump 8 and two-way piston 9, wherein, the vacuum line interface 1, pressure gauge 3, the first cold-trap 4, the second cold-trap 5,
Absorption tube 6, vacuum meter 7 and vavuum pump 8 set gradually along the vavuum pump inspiratory direction of the vacuum communicating pipeline 2, and described
Two-way piston 9 is provided between one cold-trap 4 and the second cold-trap 5, two-way is provided between the vacuum meter 7 and the vavuum pump 8
Piston 9, is provided with two-way piston 9 between the pressure gauge 3 and first cold-trap 4, the vacuum line interface 1 is 10-20
Individual, along the vavuum pump inspiratory direction order spaced set successively of the vacuum communicating pipeline 2, each described vacuum line connects
Relative set two-way piston 9 on mouth 1.
According to the present invention, the device for the ease for the treatment of vacuumize process accesses pre-treatment platform, and ensures the vacuum tube
Road interface 1 is good with the air-tightness when device for vacuumizing is connected, and the lower end of vacuum line interface 1 in the pre-treatment platform is preferred
Silicone tube is provided with, for being connected with the device for treating vacuumize process.
According to the present invention, the mode of the capillary break-up in the first collecting pipe is not particularly limited in step (iii),
For example can be by shaking the second collecting pipe 10, so as to drive the vibrations of the first collecting pipe, so that capillary break-up, discharges hair
Water sample in tubule, contacts with chromium powder, and is reacted under conditions of heating.The water sample enters according to the following formula with the reaction of chromium powder
OK：
As can be seen here, on the premise of the water sample reacts complete and ensuring equipment air-tightness is good, the hydrogen in water sample
Element is finally all converted to hydrogen, i.e., for the hydrogen isotope analyzed all from collection water sample.
According to the present invention, in order to improve the accuracy of the method for hydrogen isotope in the analysis water, and for the ease of step
Suddenly the second collecting pipe 10 described in (iv) discharges the operation of hydrogen, as shown in Fig. 2 the preferred shape in lower end of second collecting pipe 10
Into there is dip section 13, the upper end remainder of second collecting pipe 10 is extension diameter section 12, and one end of the dip section 13 seals,
The other end is connected with the extension diameter section 12.The size of the extension diameter section 12 and the dip section 13 is not particularly limited, as long as
The extension diameter section 12 is large enough to hold the first collecting pipe, and the dip section 13 can be easy to folding when release hydrogen is needed
It is disconnected, for example, the length ratio of the extension diameter section 12 and the dip section 13 can be 3-4:1, the extension diameter section 12 and described
The internal diameter ratio of dip section 13 can be 7-9:1.
In the preferred case, the length of the extension diameter section 12 of second collecting pipe 10 can be 16.5-18cm, and internal diameter can be with
It is 8-15mm；The length of the dip section 13 of second collecting pipe 10 can be 5-6cm, and internal diameter can be 1-2mm.
According to the present invention, the 3rd collecting pipe is connected with analytical equipment, for sample presentation analysis, as long as sample presentation can be ensured
Air-tightness during analysis, the 3rd collecting pipe can be glass bushing.Preferably, the 3rd collecting pipe includes
Canals of stilling and glass piston, the glass piston are used to control the connection or disconnection of the canals of stilling and analytical equipment, institute
The lower semisection for stating canals of stilling is provided with flexible pipe.The flexible pipe is not particularly limited, as long as meet having elasticity, for example
The flexible pipe can be at least one in metal hose, glass flexible pipe, rubber hose, plastic flexible pipe and silica gel hose.
According to the present invention, the size of the 3rd collecting pipe is not particularly limited, as long as can accommodate described second receiving
Collector 10, and meet when the second collecting pipe 10 is put into wherein, the dip section 13 of the second collecting pipe 10 can be received through the 3rd
The flexible pipe inner chamber of collector.According to the size of the second collecting pipe 10, the length of the 3rd collecting pipe can be 25-30cm, internal diameter
Can be 25-30mm.
According to the present invention, will during hydrogen, step (iv) are discharged when needing sample introduction to analyze for the ease of the second collecting pipe 10
The mode that second collecting pipe 10 is put into the 3rd collecting pipe is：The dip section 13 of second collecting pipe 10 is set to stretch into and through described
The flexible pipe inner chamber of the 3rd collecting pipe；The mode of hydrogen in the second collecting pipe 10 of the release is：Bend the soft of the 3rd collecting pipe
Pipe, makes to stretch into and the dip section 13 of the second collecting pipe 10 through the flexible pipe inner chamber fractures, so that hydrogen is discharged, feeding analysis
Device carries out the analysis of hydrogen isotope.
According to the present invention, the analytical equipment for analyzing hydrogen isotope can be conventionally used for analyzing various for this area
The analytical equipment of stable isotope gas, for example, the analytical equipment can be mass spectrograph.In the method that the present invention is provided,
When being analyzed to sample using mass spectrograph, the 3rd collecting pipe is accessed into mass spectrometric two-way sampling system first, open glass
Piston, makes the canals of stilling of the 3rd collecting pipe be in the state connected with mass spectrograph, then carries out vacuumize process, treats vacuum
Stabilization is 10-7-10-8Between Pa, glass piston is closed, make the canals of stilling of the 3rd collecting pipe be in enter with mass spectrometric two-way
The state that sample system disconnects, bends the flexible pipe position of the 3rd collecting pipe, and the dip section 13 of second collecting pipe 10 that fractures discharges hydrogen
Gas, then glass piston is opened, the canals of stilling of the 3rd collecting pipe is in the state connected with mass spectrometric two-way sampling system,
Complete sample introduction.
According to the present invention, the consumption of the chromium powder is not particularly limited, as long as somewhat excessive so that water sample reacts completely
, for example, the consumption of the chromium powder can meet：The weight ratio of the chromium powder and the water sample is 1000-1500：1.
According to the present invention, the heating condition of step (iii) is not particularly limited, as long as reach chromium powder being reacted with water
Required temperature, and heat time water sample total overall reaction described enough, for example, the heating operation can be in Muffle furnace
In carry out, specific heating condition can include：Heating-up temperature is 800-900 DEG C, and the heat time is 15-30min；Preferably,
The heating condition can include：Heating-up temperature is 840-860 DEG C, and the heat time is 15-20min.
In a preferred embodiment, the method for hydrogen isotope may comprise steps of in the analysis water：It is first
To first be collected after the two ends of the capillary of water sample are sealed and be put into the first collecting pipe, the first collecting pipe is then put into dress
Have in the second collecting pipe 10 of chromium powder, then the second collecting pipe 10 is passed through the vacuum line interface 1 of silicone tube and pre-treatment platform
Connection, the two-way piston 9 being correspondingly arranged on the vacuum line interface 1 that closing is connected with the second collecting pipe 10 opens vavuum pump 8,
And at the first cold-trap 4 and the second cold-trap 5 liquid nitrogen cup on set, open successively two-way piston 9 between vacuum meter 7 and vavuum pump 8,
Two-way piston 9 between two-way piston 9, the cold-trap 4 of pressure gauge 3 and first and vacuum between first cold-trap 4 and the second cold-trap 5
The two-way piston 9 being correspondingly arranged on pipe interface 1, is carried out by the vacuum of pressure gauge 3 and 7 pairs, the vacuum meter pre-treatment platform
Detection, treats that vacuum reaches 0.01Pa, using liquefied gas firelock to the second collecting pipe 10 and the vacuum line interface 1 of pre-treatment platform
Junction below, the position more than openend of the first collecting pipe that is put into inside the second collecting pipe 10 heated, make
Two collecting pipes 10 fuse and seal.The second collecting pipe 10 is shaken afterwards, so that the vibrations of the first collecting pipe are driven, so that capillary
Tracheal rupture, the water sample in release capillary.The second collecting pipe 10 is placed in Muffle furnace afterwards, with the programming rate of 15 DEG C/min,
Muffle furnace is warming up to 850 DEG C, and is kept at this temperature, chromium powder and water sample is contacted and is reacted, treat water sample total overall reaction, it is cold
But after the second collecting pipe 10 to room temperature, the second collecting pipe 10 is put into the 3rd collecting pipe, makes stretching into for second collecting pipe 10
Section 13 is stretched into and through the flexible pipe inner chamber of the 3rd collecting pipe.Then the 3rd collecting pipe is accessed into mass spectrometric two-way sample introduction system
System, opens glass piston, the canals of stilling of the 3rd collecting pipe is in the state connected with mass spectrograph, then carries out vacuumizing place
Reason, treats vacustat 10-7-10-8Between Pa, glass piston is closed, the canals of stilling of the 3rd collecting pipe is in and mass spectrum
The state that the two-way sampling system of instrument disconnects, bends the flexible pipe position of the 3rd collecting pipe, the dip section of second collecting pipe 10 that fractures
13, hydrogen is discharged, then glass piston is opened, it is in the canals of stilling of the 3rd collecting pipe and connects with mass spectrometric two-way sampling system
Logical state, completes sample introduction, carries out hydrogen isotope analysis and obtains hydrogen isotope ratio in the hydrogen as obtained in detected water sample.
According to the present invention, when carrying out the composition analysis of hydrogen isotope using mass spectrograph, using dual collector simultaneously collect by
Sample hydrogen obtained in detected water sample and standard hydrogen (hydrogen that the water sample according to international standard or national standard is prepared,
And the steel cylinder hydrogen demarcated with hydrogen obtained in these standard water samples) in1H+With2H+, sample hydrogen enters sample during sample introduction
Storehouse, standard hydrogen enters standard storehouse, is compared the analysis result of sample hydrogen and standard hydrogen by even machine computer, and directly
Connect and calculate detected water sample relative to δ D values (‰) that the hydrogen isotope of standard water sample is constituted, and with it in standard water sample
The ratio of corresponding isotope is represented, is specifically calculated according to the following formula：
In formula：SA represents detected water sample, and ST represents standard water sample.
According to the present invention, due to second collecting pipe 10 and the ingehious design of the 3rd collecting pipe, effective guarantee
Air-tightness during hydrogen occurs to be analyzed with sample introduction, and make relative to different samples are tested in traditional analysis method
Same vacuum treatment installation is used, using the means of independent encapsulation, the mutual pollution between different samples is effectively prevent, therefore,
Reduce the error of hydrogen isotope ratio in the water obtained in the step (iv) to greatest extent so that the error for-
1 ‰ -1 ‰, the error obtains the difference statistics between result and the standard value of standard water sample according to a large amount of analytical standard water samples
Draw.
Below will the present invention will be described in detail by embodiment.
In following examples, mass spectrograph is the mass spectrograph of the model Delta S of Thermo Fisher companies production, is led to
Mass spectrometric two-way sampling system (Dual-Inlet) is crossed to H to be measured2Sample is detected, carried out under 7000mV signal intensities
Sample determination, each sample test 6 times, averages.
In following embodiment, the international reference materials is standard average sea water (Standard Mean Ocean
Water, SMOW), δ D values (‰) of detected water sample represent the hydrogen isotope composition of detected water sample, and with it to the average sea of standard
The ratio of corresponding isotope is represented in foreign-water (V-SMOW), is specifically calculated according to the following formula：
In formula, SA representative samples, SMOW represents standard average sea water.
Embodiment 1-10
To be collected after the two ends of the capillary of water sample are sealed and be put into the first collecting pipe, then by the first collecting pipe
It is put into the second collecting pipe 10 equipped with chromium powder, then by the second collecting pipe 10 by silicone tube and the vacuum line of pre-treatment platform
Interface 1 is connected, the two-way piston 9 being correspondingly arranged on the vacuum line interface 1 that closing is connected with the second collecting pipe 10, opens vacuum
Pump 8, and the liquid nitrogen cup on set at the first cold-trap 4 and the second cold-trap 5, the two-way opened successively between vacuum meter 7 and vavuum pump 8 are lived
Plug the 9, first cold-trap 4 and the second cold-trap 5 between two-way piston 9, the cold-trap 4 of pressure gauge 3 and first between two-way piston 9 and
The two-way piston 9 being correspondingly arranged on vacuum line interface 1, by pressure gauge 3 and the vacuum of 7 pairs, the vacuum meter pre-treatment platform
Detected, treated that vacuum reaches 0.01Pa, using liquefied gas firelock to the second collecting pipe 10 and the vacuum line of pre-treatment platform
Position below the junction of interface 1, more than the openend of the first collecting pipe that is put into inside the second collecting pipe 10 is heated,
The second collecting pipe 10 is set to fuse and seal.The second collecting pipe 10 is shaken afterwards, so that the vibrations of the first collecting pipe are driven, so that
Capillary break-up, the water sample in release capillary.The second collecting pipe 10 is placed in Muffle furnace is afterwards heated, make chromium powder and water sample
Contact and react, treat water sample total overall reaction, after the second collecting pipe 10 to room temperature of cooling, the second collecting pipe 10 is put into the 3rd collection
Pipe, makes the dip section 13 of second collecting pipe 10 stretch into and through the flexible pipe inner chamber of the 3rd collecting pipe.Then by the 3rd
Collecting pipe accesses mass spectrometric two-way sampling system by three-way connection, then carries out vacuumize process, treats that vacustat exists
10-7Pa, rotatory sealing piston makes sealing piston be in the state disconnected with mass spectrometric two-way sampling system, and bending the 3rd is received
The flexible pipe position of collector, the dip section 13 of second collecting pipe 10 that fractures discharges hydrogen, then rotatory sealing piston, makes sealing piston
State in being connected with mass spectrometric two-way sampling system, completes sample introduction, carries out hydrogen isotope analysis and obtains by detected water sample
Hydrogen isotope ratio in obtained hydrogen, so as to obtain suitable with hydrogen isotope ratio in hydrogen obtained in detected water sample being tested
Hydrogen isotope ratio in water sample.
Hydrogen isotope ratio in embodiment 1-10 in the species of each material used, consumption and test result and water sample
Standard value it is as shown in table 1.Concrete analysis result in embodiment 1-10 to sample test 6 times is as shown in table 2.
Comparative example 1-10
According to《Metallic zinc method determines natural water, mineral inclusion and hydrogeneous mineral hydrogen isotope technique study》(Zhou Yamin,
Mineral products and geology, 1995 (S1):The method of the hydrogen isotope in 398-403.) in test natural water, using on-line method pair and in fact
Identical water sample is tested in applying a 1-10.
Hydrogen isotope ratio in comparative example 1-10 in the species of each material used, consumption and test result and water sample
Standard value it is as shown in table 1.
Table 1
Table 2
Be can be seen that by the result of Tables 1 and 2 and use the method for present invention offer to be analyzed hydrogen isotope in water
When, using the means of independent encapsulation, to effectively prevent and test different samples in traditional analysis method and use same application of vacuum
The mutual pollution caused during device, the degree of accuracy of hydrogen isotope ratio data is higher and reappearance is preferable in the final water for obtaining.
Method provided by the present invention also has the advantages that water sample consumption is few, reaction speed is fast, high precision and environment are friendly.Additionally, by
The method that the present invention is provided simplifies sample preparation flow, improves the preparation efficiency of sample, has saved the pre-treatment time, disclosure satisfy that
The demand of Industrial Analysis batch samples.
And make water sample in vapour form by the zinc stove at 400 DEG C using two cold-traps in comparative example 1-8, then will produce
Hydrogen charcoal absorption be collected in and make mass spectral analysis in gas sample pipe, operating process complexity is cumbersome, and hydrogen is same in determining water
During the element ratio of position, water sample consumption is big, the data precision is relatively low, reappearance is poor.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited thereto.In skill of the invention
In art concept, technical scheme can be carried out various simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (10)
1. it is a kind of analyze water in hydrogen isotope method, it is characterised in that the described method comprises the following steps：
I () will be collected after the two ends of the capillary of water sample are sealed and be put into the first collecting pipe；
(ii) by the first collecting pipe in step (i) be put into the second collecting pipe (10) equipped with chromium powder and carry out vacuumize process it
Afterwards, the second collecting pipe (10) is sealed；
(iii) make the capillary break-up in the first collecting pipe, under conditions of heating, make chromium powder in the second collecting pipe (10) with
Water sample in capillary reacts；
(iv) treat that the chromium powder in step (iii) terminates with water sample reaction, the second collecting pipe (10) is put into the 3rd collecting pipe, afterwards
3rd collecting pipe is connected with analytical equipment, the hydrogen in the second collecting pipe of release (10), carries out hydrogen isotope analysis and obtain water
Middle hydrogen isotope ratio.
2. method according to claim 1, wherein, the vacuumize process of step (ii) is processed using pre-treatment platform,
The pre-treatment platform includes：It is vacuum line interface (1), vacuum communicating pipeline (2), pressure gauge (3), the first cold-trap (4), second cold
Trap (5), absorption tube (6), vacuum meter (7), vavuum pump (8) and two-way piston (9), wherein, the vacuum line interface (1), pressure
Power meter (3), the first cold-trap (4), the second cold-trap (5), absorption tube (6), vacuum meter (7) and vavuum pump (8) connect along the vacuum
The vavuum pump inspiratory direction on siphunculus road (2) is set gradually, and two-way is provided between first cold-trap (4) and the second cold-trap (5)
Piston (9), is provided with two-way piston (9) between the vacuum meter (7) and the vavuum pump (8), the pressure gauge (3) with it is described
Two-way piston (9) is provided between first cold-trap (4), the vacuum line interface (1) is 10-20, is connected along the vacuum
The vavuum pump inspiratory direction on siphunculus road (2) order spaced set, relative set on each described vacuum line interface (1) successively
Two-way piston (9).
3. method according to claim 1, wherein, the error of hydrogen isotope ratio in the water obtained in the step (iv)
It is -1 ‰ -1 ‰.
4. method according to claim 1, wherein, first collecting pipe is the quartz ampoule of flat mouth round bottom.
5. method according to claim 1, wherein, second collecting pipe (10) includes extension diameter section (12) and dip section
(13), one end sealing of the dip section (13), the other end connects with the extension diameter section (12), the extension diameter section (12) and described
The length ratio of dip section (13) is 3-4:1, the internal diameter ratio of the extension diameter section (12) and the dip section (13) is 7-9:1.
6. method according to claim 1, wherein, the 3rd collecting pipe is glass bushing, including canals of stilling and glass
Glass piston, the glass piston is used to control the connection or disconnection of the canals of stilling and analytical equipment, the canals of stilling
Lower semisection is provided with flexible pipe.
7. method according to claim 1, wherein, the second collecting pipe (10) is put into the 3rd collecting pipe in step (iv)
Mode is：The dip section (13) of second collecting pipe (10) is set to stretch into and through the flexible pipe inner chamber of the 3rd collecting pipe；
The mode of the hydrogen in the release the second collecting pipe (10) is：The flexible pipe of the 3rd collecting pipe is bent, is made to stretch into and is run through
The dip section (13) of second collecting pipe (10) of the flexible pipe inner chamber fractures, so as to discharge hydrogen.
8. the method according to any one in claim 1-7, wherein, the weight ratio of the chromium powder and the water sample is
1000-1500：1.
9. the method according to any one in claim 1-7, wherein, taking out for step (ii) really is processed as making the second collection
The vacuum of pipe reaches 10-7-10-8Pa。
10. the method according to any one in claim 1-7, wherein, the heating condition of step (iii) includes：Heating
Temperature is 800-900 DEG C, and the heat time is 15-30min；
Preferably, the heating condition of step (iii) includes：Heating-up temperature is 840-860 DEG C, and the heat time is 15-20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710168894.9A CN106769346B (en) | 2017-03-21 | 2017-03-21 | Method for analyzing hydrogen isotopes in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710168894.9A CN106769346B (en) | 2017-03-21 | 2017-03-21 | Method for analyzing hydrogen isotopes in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106769346A true CN106769346A (en) | 2017-05-31 |
| CN106769346B CN106769346B (en) | 2020-02-07 |
Family
ID=58966374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710168894.9A Active CN106769346B (en) | 2017-03-21 | 2017-03-21 | Method for analyzing hydrogen isotopes in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106769346B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108072713A (en) * | 2017-11-22 | 2018-05-25 | 中国科学院地质与地球物理研究所 | The method of hydrogen isotope in on-line analysis fluid inclusion water |
| 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 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786701A (en) * | 2004-12-10 | 2006-06-14 | 上海化工研究院 | Method for determining content of (18) 0 isotope in water |
| JP2010208927A (en) * | 2009-03-12 | 2010-09-24 | Osaka Univ | Method for producing at least one of deuterium (d2) and hydrogen deuteride (hd) and formic acid decomposition catalyst to be used therein |
| CN103091137A (en) * | 2011-11-04 | 2013-05-08 | 核工业北京地质研究院 | Carbon and hydrogen isotope analysis pre-treating device for gas and liquid inclusion in mineral |
| CN103439164A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院新疆生态与地理研究所 | Quick plant or soil water vacuum-extraction method based on microwave heating |
| CN103645239A (en) * | 2013-12-20 | 2014-03-19 | 中国科学院地质与地球物理研究所 | Method and device for analyzing sulfur isotopes in sulfate radical |
| CN104181245A (en) * | 2014-08-22 | 2014-12-03 | 中国科学院地质与地球物理研究所 | Method for analyzing hydrogen isotope in water of fluid inclusion |
| CN104215728A (en) * | 2014-08-22 | 2014-12-17 | 中国科学院地质与地球物理研究所 | Fluid inclusion water hydrogen isotope analysis system |
| CN106092691A (en) * | 2016-07-16 | 2016-11-09 | 中国科学院寒区旱区环境与工程研究所 | Solid hydrogen-containing sample hydrogen isotope on-line sample preparation facilities |
| CN205786017U (en) * | 2016-07-03 | 2016-12-07 | 中国科学院寒区旱区环境与工程研究所 | Nitrous oxide gas nitrogen and oxygen isotopes analyzes front device |
-
2017
- 2017-03-21 CN CN201710168894.9A patent/CN106769346B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1786701A (en) * | 2004-12-10 | 2006-06-14 | 上海化工研究院 | Method for determining content of (18) 0 isotope in water |
| JP2010208927A (en) * | 2009-03-12 | 2010-09-24 | Osaka Univ | Method for producing at least one of deuterium (d2) and hydrogen deuteride (hd) and formic acid decomposition catalyst to be used therein |
| CN103091137A (en) * | 2011-11-04 | 2013-05-08 | 核工业北京地质研究院 | Carbon and hydrogen isotope analysis pre-treating device for gas and liquid inclusion in mineral |
| CN103439164A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院新疆生态与地理研究所 | Quick plant or soil water vacuum-extraction method based on microwave heating |
| CN103645239A (en) * | 2013-12-20 | 2014-03-19 | 中国科学院地质与地球物理研究所 | Method and device for analyzing sulfur isotopes in sulfate radical |
| CN104181245A (en) * | 2014-08-22 | 2014-12-03 | 中国科学院地质与地球物理研究所 | Method for analyzing hydrogen isotope in water of fluid inclusion |
| CN104215728A (en) * | 2014-08-22 | 2014-12-17 | 中国科学院地质与地球物理研究所 | Fluid inclusion water hydrogen isotope analysis system |
| CN205786017U (en) * | 2016-07-03 | 2016-12-07 | 中国科学院寒区旱区环境与工程研究所 | Nitrous oxide gas nitrogen and oxygen isotopes analyzes front device |
| CN106092691A (en) * | 2016-07-16 | 2016-11-09 | 中国科学院寒区旱区环境与工程研究所 | Solid hydrogen-containing sample hydrogen isotope on-line sample preparation facilities |
Non-Patent Citations (2)
| Title |
|---|
| 张琳等: "水中氢氧同位素不同分析方法的对比", 《岩矿测试》 * |
| 李洪伟等: "密封石英管法快速分析包裹体中氢同位素", 《质谱学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108072713A (en) * | 2017-11-22 | 2018-05-25 | 中国科学院地质与地球物理研究所 | The method of hydrogen isotope in on-line analysis fluid inclusion water |
| CN108072713B (en) * | 2017-11-22 | 2018-10-16 | 中国科学院地质与地球物理研究所 | The method of hydrogen isotope in on-line analysis fluid inclusion water |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106769346B (en) | 2020-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103822811B (en) | A kind of test organism class sample 14the pre-treating method of C abundance and equipment | |
| CN104181245B (en) | A kind of hydrogen isotope analysis method in fluid inclusion water | |
| CN102636595A (en) | Continuous gas in-tube solid phase microextraction device combined with gas chromatography for use | |
| CN106769346A (en) | The method of hydrogen isotope in analysis water | |
| CN104215728A (en) | Fluid inclusion water hydrogen isotope analysis system | |
| CN201392289Y (en) | Water sample extractive distillation apparatus | |
| CN109946407A (en) | A kind of mineral inclusion water sample extraction element for H isotope analysis | |
| CN106092691A (en) | Solid hydrogen-containing sample hydrogen isotope on-line sample preparation facilities | |
| CN111024483A (en) | Chlorosilane pretreatment system and method for detecting impurity content in chlorosilane | |
| CN102998157A (en) | Device for extracting acid volatile sulfide in geological sample | |
| CN206648999U (en) | A kind of device suitable for surface plate original position SPME measure | |
| CN207379974U (en) | The analysis system of not oxygen-containing mineral inclusion water oxygen isotopics | |
| CN210474850U (en) | Insert formula adsorption tube analytic device soon | |
| CN106525514A (en) | Atmosphere vapor collection vacuum transfer device | |
| CN208654232U (en) | Simulate coal body hydraulic fracturing complex resistance measuring system | |
| CN203333712U (en) | Sealable annealing pipe | |
| CN209502964U (en) | A kind of automatic high temperature and high pressure gas reaction nano metal composite material prepares furnace | |
| CN206161390U (en) | Vacuum transfer device is collected to atmosphere steam | |
| CN206161642U (en) | Extraction and desorption device | |
| CN206479395U (en) | A kind of continuous liquid adding type clears up instrument | |
| CN101710036B (en) | Puncture device of gold pipe and collection device of trace hydrogen sulfide generated by thermal simulation in gold pipe | |
| CN204666581U (en) | The online characterization system of a kind of reaction in-situ | |
| CN105319120B (en) | The NO reforming units of Vehicular exhaust detection | |
| CN208921655U (en) | Carbon and hydrogen isotope oil-free valve analysis system for mineral fluid inclusion | |
| CN209247711U (en) | A kind of stoste processing unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |