CN108072713B - The method of hydrogen isotope in on-line analysis fluid inclusion water - Google Patents
The method of hydrogen isotope in on-line analysis fluid inclusion water Download PDFInfo
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- CN108072713B CN108072713B CN201711175677.9A CN201711175677A CN108072713B CN 108072713 B CN108072713 B CN 108072713B CN 201711175677 A CN201711175677 A CN 201711175677A CN 108072713 B CN108072713 B CN 108072713B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/08—Preparation using an enricher
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Abstract
The present invention relates to Stable Isotopic Analysis technical field, the method that discloses hydrogen isotope in a kind of on-line analysis fluid inclusion water, which is characterized in that the described method comprises the following steps：(I) so that the water in fluid inclusion is discharged using dynamic flash burn method and carry out gaseous mixture of the reduction reaction generation containing hydrogen；(II) enriching apparatus is used to be enriched with the gaseous mixture containing hydrogen generated in step (I)；(III) gas chromatographic column is utilized to isolate hydrogen in the gaseous mixture containing hydrogen of enrichment from step (II)；(IV) hydrogen for isolating step (III) imports the ion source of isotope-ratio mass spectrometer by open split type interface, carries out the analysis of hydrogen isotope in fluid inclusion water and obtains hydrogen isotope ratio.This method can meet requirement of the mass spectrometer ion source to gas flow and the sample gas of generation is imported isotope-ratio mass spectrometer to the maximum extent, and detection limit is low, and analytical error is small, and accuracy is high.
Description
Technical field
The present invention relates to Stable Isotopic Analysis technical fields, and in particular to hydrogen in a kind of on-line analysis fluid inclusion water
The method of isotope.
Background technology
Fluid inclusion in diagenetic mineral be Diagenesis And Mineralization fluid in crystallizable mineral growth course because of crystal growth machine
System, the speed of growth, certain (a little) concentration of component change or the influence of the factors such as multi phase interface interaction, and is wrapped in
Diagenesis And Mineralization stream in mineral lattice defect or cave nest, still being sealed up for safekeeping in host so far and have the boundary of phase with host
Body is the Diagenesis And Mineralization primary sample preserved so far.In mineral deposit and dyke rock in fluid inclusion hydrogen isotope research for visit
Fluid inclusion natures, source, evolution and the origin cause of formation is begged for have great importance.
It is mainly in the world at present high-frequency heating U/ to the analysis method and means of hydrogen isotope composition in fluid inclusion
Zn/Cr conversion methods.Quartz tube furnace thermal explosion method is to obtain the classical way of water in fluid inclusion, it is added by quartz tube type
Hot stove heats sample, the process for making the liquid phase in fluid inclusion form larger pressure, and then being released from rock.
When analyzing hydrogen isotope in fluid inclusion water, first, Fluid inclusions are discharged by high-temperature heating under vacuum
Water in body sample then allows H by redox reaction2O is converted into H2, finally by the Static Analysis Method of two-way sample introduction
Hydrogen isotope composition is analyzed on gas isotope ratio mass spectrograph.Hydrogen isotope ratio is analyzed in traditional fluid inclusion water
Method is off-line analysis method, and in off-line analysis system, sample bursting device, water sample collection device and pyroreaction pipe difference are only
It erects and sets.Traditional analysis carries out primary accurately hydrogen isotope analysis and the amount of H in sample is required to reach 10-4~10-6It rubs
Therefore you greatly and need the error of the very low solid sample conventional method analysis of micro water sample and water content very much
A large amount of sample.Fluid inclusion hydrogen isotope analysis is needed be more than 2g sample, this results in conventional method for micro-
Hydrogen isotope can not be completed to analyze in amount fluid inclusion water.
Have recently emerged a kind of analysis method (TC/EA- of new Pintsch process/Element and isotope on-line continuous stream
MS), the H in this method successful analysis micro water sample and alcohol sample, micro organic sample and enhydrite is same
Position element composition.This continuous flow analysis method, which can be analyzed, contains about 10-9The hydrogen isotope composition of the sample of mole H, analysis
Outer precision is ± 1 ‰~± 10 ‰ (1 σ), relative to conventional method, not only reduces analytical error, decreases needed for analysis
The amount of sample.Device for implementing the method structural schematic diagram is as shown in Figure 1, first, sample is sent through automatic sampling apparatus
Enter in high-temperature cracking furnace, occur to crack and generate the gaseous mixture containing hydrogen, through chromatography, then obtained hydrogen will be purified
Stable isotope is imported than in mass spectrometric ion source, neutral hydrogen atom is ionized to the different charged particle of mass-to-charge ratio, through electricity
Magnet quality accelerates, and the ion of different quality is separated into the different ion stream of amount of deflection, is finally received and is remembered by Faraday cup
The analysis result of sample gas analysis result and reference gas is subject to by separated several beam ions and its intensity by online process by record
It compares, obtains hydrogen isotope ratio in fluid inclusion water.Since fluid inclusion is relative to other material compositions complexity, use
The method analysis micro fluid inclusion enclave hydrogen isotope world there is no report.Above-mentioned Pintsch process/Element and isotope connects online
The analysis method of afterflow is for when analyzing organic sample, usually firstly the need of in reduction furnace, using vitreous carbon to organic sample
The functional groups such as hydroxyl restored to prepare generation hydrogen, and fluid inclusion Pintsch process will produce some other gases
(such as hydrocarbon gas), it is possible to can not be reacted with the vitreous carbon being equipped in reduction furnace, then go through gas isotope mass spectrograph
It is interior, the final service life and the quality of data for influencing ion source.
General elemental analyser carrier gas in the analysis test process of Pintsch process/Element and isotope on-line continuous stream
Flow control is in 80~100mL/min or so, if being directly entered mass spectrometric ion source, instrument vacuum will certainly be caused to have very
It is big to reduce, it is difficult to realize to isotope high-precision measuring, while excessive gas shock can also influence the longevity of filament in ion source
Life, so general way is only to allow a certain amount of gas to enter ion source by special interface technology.In this method, element
Analyzer (EA) is connect with gas isotope mass spectrograph (IRMS) by special interface ConFlo, and principle is illustrated：Such as Fig. 2 institutes
Show, when there is the gas flow gas isotope mass spectrograph of 80mL/min, wherein there is the gas of 72mL/min to be split, it is only surplus
The gas of remaining 8mL/min enters the open split type interface (open split) of ConFlo, and herein with another way helium mix
(the road helium is mainly used for excluding the air in open split type interface), then a capillary passes through the pressure inside and outside ion source
Sample gas is imported ion source by force difference, and gas flow is only 0.5mL/min in the capillary at this time, it is possible thereby to substantially reduce gas
Body flow, to avoid the interference to ion source.The shortcomings that this design is that there is no the gases for generating sample to be all sent into
Ion source, only very small part gas are utilized.So in order to which the detection for meeting isotope mass spectrometer limits (ion intensity of flow
In 2V or more), it is necessary to need a large amount of sample.Therefore, a kind of mass spectrometer ion source that can meet is selected to want gas flow
It asks, and the sample gas of generation can be sent into isotope-ratio mass spectrometer to the maximum extent, substantially reduce the detection limit of instrument,
The high-precision on-line analysis for being achieved in the hydrogen isotope ratio containing micro-example is hydrogen isotope analysis in fluid inclusion water
One, field urgent problem to be solved.
Invention content
The purpose of the invention is to overcome in existing fluid inclusion water existing for hydrogen isotope off-line analysis technology
Analytical error is big, sample consumption is more, experimentation is cumbersome, efficiency is low and existing Pintsch process/Element and isotope is online
The analysis method of continuous flow is not suitable for the on-line analysis of hydrogen isotope and the Pintsch process/member in fluid inclusion water
It is low that element can not maximally utilise sample gas with the analysis method of isotope on-line continuous stream, instrument detects limit for height, precision
The defects of, micro fluid packet may be implemented in the method for providing hydrogen isotope in a kind of on-line analysis fluid inclusion water, this method
The quick analysis for wrapping up in hydrogen isotope in body water is solved the problems, such as to be difficult to analyze when fluid inclusion water content is low, and is analyzed
Process is simply controllable, easy to operate, can maximally utilise sample gas, and instrument detection limits low, high sensitivity, and analysis misses
Difference is small, and accuracy is high.
To achieve the goals above, one aspect of the present invention provides hydrogen isotope in a kind of on-line analysis fluid inclusion water
Method the described method comprises the following steps：
(I) in the reaction tube for being filled with chromium powder, the water in fluid inclusion is made to discharge and carry out using dynamic flash burn method
Redox reaction generates the gaseous mixture containing hydrogen；
(II) enriching apparatus is used to be enriched with the gaseous mixture containing hydrogen generated in step (I)；
(III) gas chromatographic column i is utilized to isolate hydrogen in the gaseous mixture containing hydrogen of enrichment from step (II)；
(IV) hydrogen for isolating step (III) imports isotope-ratio mass spectrometer by open split type interface j
Ion source carries out the analysis of hydrogen isotope in fluid inclusion water and obtains hydrogen isotope ratio,
Wherein, the enriching apparatus includes eight ways valve d, sample cell g and cooling pit, and the eight ways valve d is provided with for connecing
Interface, the gaseous mixture containing hydrogen for step (II) to be enriched with for receiving the gaseous mixture containing hydrogen generated in step (I)
It exports to the interface of gas chromatographic column i and for being connected to the interface being arranged with the both ends of the sample cell g, the eight ways valve d is also
It is provided with switch knob, two kinds of mode of communicating of sampling and sample introduction for switching the eight ways valve d are arranged on the sample cell g
Have and fill out shape in helical form sample loop h, the sample loop h and have a porous material, the sample loop h is can freely be put into or removal method
It is arranged in cooling pit, press-fit connector k is provided in the open split type interface j.
This method is by by the Pintsch process pipe of elemental analyser again filler design optimization, with gas isotope mass spectrograph
Combination reduces the isotopic fractionation for being transformed into hydrogen molecule, improves solid sample hydrogen isotope test quality, makes it suitable for
The analysis of hydrogen isotope in micro fluid inclusion water, and can meet requirement of the mass spectrometer ion source to gas flow and
The sample gas of generation can be sent into isotope-ratio mass spectrometer to the maximum extent, greatly reduce the detection limit of instrument, carry
The high sensitivity of instrument.
Description of the drawings
Fig. 1 is the element for analyzing the composition of the hydrogen isotope in micro water sample, organic sample and enhydrite
The structural schematic diagram of analyzer-ConFlo- isotope-ratio mass spectrometer combined apparatus；
Fig. 2 is that the ConFlo open split types in elemental analyser-ConFlo- isotope-ratio mass spectrometer combined apparatus connect
Gas distribution schematic diagram in mouthful；
Fig. 3 is the structural representation of the combined apparatus of hydrogen isotope in the on-line analysis fluid inclusion water that the present invention uses
Figure；
Flow of Goods and Materials path when Fig. 4 is the sampling mode of communicating and sample introduction mode of communicating for the eight ways valve d that the present invention uses
Schematic diagram；
Fig. 5 is the structural schematic diagram for the press-fit connector that the present invention uses.
Reference sign
A, isotope-ratio mass spectrometer a1, ion source
A2, electromagnet a3, Faraday cup
B, ConFlo types interface b1, open split type interface
C, elemental analyser c1, high-temperature cracking furnace
C2, gas chromatographic column d, eight ways valve
E, reaction tube f, solid autosampler
G, sample cell h, sample loop
I, gas chromatographic column j, open split type interface
K, press-fit connector 1, first interface
2, second interface 3, third interface
4, the 4th interface 5, the 5th interface
6, the 6th interface 7, the 7th interface
8, the 8th interface 1#, the first capillary
2#, the second capillary 3#, third capillary
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, in the absence of explanation to the contrary, the noun of locality used such as " upper and lower " typically refer to relative to
Orientation of the present invention for the structural schematic diagram of the device of hydrogen isotope in on-line analysis fluid inclusion water." interior,
Outside " limited relative to the practical structures of the device of hydrogen isotope in the fluid inclusion water of the present invention for on-line analysis
It is fixed.
As previously mentioned, the present invention provides a kind of method of hydrogen isotope in on-line analysis fluid inclusion water, the side
Method includes the following steps：
(I) in the reaction tube for being filled with chromium powder, the water in fluid inclusion is made to discharge and carry out using dynamic flash burn method
Redox reaction generates the gaseous mixture containing hydrogen；
(II) enriching apparatus is used to be enriched with the gaseous mixture containing hydrogen generated in step (I)；
(III) gas chromatographic column i is utilized to isolate hydrogen in the gaseous mixture containing hydrogen of enrichment from step (II)；
(IV) hydrogen for isolating step (III) imports isotope-ratio mass spectrometer by open split type interface j
Ion source carries out the analysis of hydrogen isotope in fluid inclusion water and obtains hydrogen isotope ratio,
Wherein, the enriching apparatus includes eight ways valve d, sample cell g and cooling pit, and the eight ways valve d is provided with for connecing
Interface, the gaseous mixture containing hydrogen for step (II) to be enriched with for receiving the gaseous mixture containing hydrogen generated in step (I)
It exports to the interface of gas chromatographic column i and for being connected to the interface being arranged with the both ends of the sample cell g, the eight ways valve d is also
It is provided with switch knob, two kinds of companies of sampling (LOAD MODE) and sample introduction (INJECT MODE) for switching the eight ways valve d
Logical mode is provided on the sample cell g and fills out shape in helical form sample loop h, the sample loop h and have porous material, the sample
Ring h with can freely be put into or removal method be arranged in cooling pit, be provided in the open split type interface j press-fit connection
Head (press-fit connector) k.
According to the present invention, in step (I), the process packet for making the water in fluid inclusion discharge using dynamic flash burn method
It includes：Fluid inclusion is packaged using tin can or silver cup, then the packaged fluid inclusion through solid automatically into
Sample device enters in reaction tube, controls the temperature of the reaction tube to 900-1100 DEG C, in the presence of the first carrier gas, is dodged
Combustion, makes fluid inclusion by thermal spalling, and release the water in fluid inclusion.
According to the present invention, not aqueous and protium in the tin can or silver cup ingredient will not be to final hydrogen isotope ratio
Test result have an impact.
According to the present invention, first carrier gas is used to sample gas being carried to enriching apparatus, the choosing of first carrier gas
Select that there is no particular limitation, if not with it is each anti-during dynamic flash burn process described in step (I) and the reduction reaction
It answers object and reaction product to react, and does not influence final isotope-ratio mass spectrometer to hydrogen isotope in fluid inclusion water
The analysis of composition, it is preferable that first carrier gas is helium.
According to the present invention, the fluid inclusion is carried out by the process of thermal spalling in the reaction tube for being filled with chromium powder, institute
Fluid inclusion is stated directly to be contacted with the chromium powder loaded in reaction tube by the water that dynamic flash burn discharges after by thermal spalling.
According to the present invention, in order to further increase the temperature of the dynamic flash burn process, be more advantageous to it is described with tin can or
The abundant burning of the packaged fluid inclusion of silver cup bursts, the process of the dynamic flash burn preferably under conditions of noting oxygen into
Row.
According to the present invention, when the fluid inclusion packaged with tin can or silver cup under conditions of noting oxygen into Mobile state
When flash burn, the flow of the oxygen can be selected according to the dosage of reality into the fluid inclusion of Mobile state flash burn, preferably
In the case of, the condition of the note oxygen includes：Note oxygen flow is 15-30mL/min, and the note oxygen time is 20-60s.If the stream of oxygen
Amount is less than 15mL/min, the explosion of fluid inclusion sample can be caused insufficient, remaining ash content, which is retained in reaction tube, to be influenced
The Measurement results of next sample can influence the fluid inclusion warp if the flow of oxygen is higher than 30mL/min
The carry out degree that the gas generated after dynamic flash burn carries out the redox reaction generation hydrogen of next step is crossed, sample can be equally influenced
The Measurement results of product.When under conditions of noting oxygen into Mobile state flash burn, tin can or silver cup react the heat discharged with oxygen
Temperature in reaction tube can be made further to increase, it is preferable that the note oxygen condition satisfaction makes flash ignition temperature reach 1700-1800
DEG C, be more advantageous in this way the fluid inclusion packaged with tin can or silver cup it is abundant explosion and fluid inclusion in water
Release.
According to the present invention, the process of the redox reaction includes：Under heating conditions, fluid inclusion is made to discharge
Water contacted with the chromium powder loaded in reaction tube.The water of the fluid inclusion release carries out according to the following formula with reacting for chromium powder：
According to the present invention, it is required that the condition of the heating needs the water for reaching chromium powder and fluid inclusion release to react
Temperature, heating temperature is too high or too low, can all influence the isotope analysis knot for finally analyzing hydrogen in the fluid inclusion water
Fruit, and the heating time water sample total overall reaction described enough, the condition of the heating preferably include：Heating temperature is 900-1100
DEG C, heating time 5-12min.In method provided by the invention, the fluid inclusion is into Mobile state flash burn and by thermal explosion
It splits required temperature and equally meets the water of chromium powder and fluid inclusion release and temperature needed for redox reaction, and institute occurs
Fluid inclusion is stated into Mobile state flash burn and after by thermal spalling, the temperature in the reaction tube can drop back to rapidly to pre-setting
Temperature, reacting that the water that chromium powder and fluid inclusion discharge can't occur adversely affect, therefore, the fluid packet
It wraps up in body to be carried out at the same time in the reaction tube by the process of process and reduction reaction that thermal spalling discharges water, to realize simultaneously
The purpose of row experiment.
According to the present invention, the solid autosampler using unique turntable design, can accommodate simultaneously 40 it is to be analyzed
The storage of fluid inclusion sample, and can realize automatic continued inlet according to the time interval pre-set.In order to provide
Sufficient reducing agent, meeting the chromium powder loaded in reaction tube to the maximum extent will can repeatedly be connected by the solid autosampler
The water that all fluid inclusion samples to be analyzed that continuous sample introduction enters in reaction tube are discharged after by thermal spalling by dynamic flash burn is complete
Portion is reduced into hydrogen, and the used in amounts of the chromium powder is higher than theoretical reaction dosage, under preferable case, the amount of fill of the chromium powder with
The weight ratio of the dosage of the fluid inclusion is 500-1500：1.
According to a kind of specific embodiment of the present invention, when the dosage of each fluid inclusion sample to be analyzed is
100mg, when the amount of fill of chromium powder is 100g in the reaction tube, enough by up to a hundred fluid inclusion samples release to be analyzed
Water Restore All is hydrogen.
According to the present invention, the chromium oxide and unreacted chromium powder that are generated after chromium powder progress redox reaction in order to prevent
The water in fluid inclusion is hindered to carry out the smoothness that redox reaction generates the flowing of the gaseous mixture containing hydrogen with chromium powder,
The reaction bottom of the tube is preferably additionally provided with quartz film, and the quartz film is made of quartz fibre element, has good heat-resisting steady
Qualitative and gas permeability can ensure that the gaseous mixture containing hydrogen contains hydrogen under the carrying of the first carrier gas described in smooth flow direction
The enriching apparatus of the gaseous mixture of gas.
According to the present invention, contain hydrogen to ensure that the water in fluid inclusion and chromium powder carry out redox reaction generation
Gaseous mixture all import subsequent enriching apparatus, first carrier gas is preferably injected with the flow of 80-100mL/min and is reacted
Pipe.
According to the present invention, in step (II), the enrichment of the gaseous mixture containing hydrogen to being generated in step (I) passes through switching
Two kinds of mode of communicating of sampling and sample introduction of eight ways valve d in the enriching apparatus carry out.
According to the present invention, as shown in figure 4, the eight ways valve d is provided with the interface 8 of first interface 1~the 8th, each interface with
Its adjacent interface selects a connection, and when the eight ways valve d is connected in a manner of sampling or sample introduction respectively, the eight ways valve d's is each
The connected relation of interface is respectively：
When the mode of communicating of the eight ways valve d is sampling mode of communicating, as shown in Fig. 4 (A), the of the eight ways valve d
Two interfaces 2 are connected to third interface 3, and the 4th interface 4 is connected to the 5th interface 5, and the 6th interface 6 is connected to the 7th interface 7, and the 8th
Interface 8 is connected to first interface 1；
When the mode of communicating of the eight ways valve d is sample introduction mode of communicating, as shown in Fig. 4 (B), the of the eight ways valve d
Two interfaces 2 are connected to first interface 1, and the 4th interface 4 is connected to third interface 3, and the 6th interface 6 is connected to the 5th interface 5, and the 8th
Interface 8 is connected to the 7th interface 7.
According to the present invention, it is provided on the sample cell g in helical form sample loop h, the sample loop h and is filled with porous material
Material.The porous material is preferably the porous material with adsorbed hydrogen function, for example, the porous material can be porous carbon
Sill and porous silicon-base material, it is preferable that the porous material be activated carbon, 5A molecular sieves and 13A molecular sieves at least
One kind, it is highly preferred that the porous material is 5A molecular sieves.In this way, when the mixing containing hydrogen generated in step (I)
When air-flow is through the sample loop h, it can be adsorbed in the porous material in the sample loop h.
According to the present invention, in order to further promote the porous material to containing hydrogen into what is generated in step (I)
Gaseous mixture absorption, the enriching apparatus further includes cooling pit, the sample loop h with can freely be put into or removal method be arranged
In cooling pit.When the sample loop h is placed in the cooling pit, the pressure that is placed in the sample loop h in the cooling pit
It is minimized by force, and then so that the higher mixed airflow containing hydrogen of temperature generated in step (I) is passed through and be in cooling pit
In sample loop h when, be fully adsorbed in the duct of the porous material in the sample loop h.
According to the present invention, the enrichment of the gaseous mixture containing hydrogen generated in the step (I) for convenience meets simultaneously
Pressure in the sample loop h can be reached to the porous material to coming from the mixing containing hydrogen generated in step (I)
The required temperature of the absorption pressure of gas, the cooling pit is preferably the Dewar bottle equipped with coolant, and the cooling pit is further excellent
It is selected as the Dewar bottle equipped with liquid nitrogen.
According to the present invention, in order to further regulate and control the gas stream of the gaseous mixture containing hydrogen generated in step (I)
Amount, the internal diameter of the sample cell g is preferably 0.4-0.8mm, and the sample cell g described in this way contains to coming from generation in step (I)
The gaseous mixture of hydrogen can play the role of throttling.In order to ensure the mechanical strength of the sample cell g, the wall of the sample cell g
Thickness is preferably 0.2-0.5mm.In order to extend the gaseous mixture containing hydrogen generated in step (I) as possible in the sample cell
Circulation path length in g makes the gaseous mixture containing hydrogen fully be adsorbed by the porous material, while being convenient for the sample
Product ring h can be freely put into or removal method be arranged in cooling pit, the sample loop h is located at the middle part of sample cell g, by sample
Winding 1-3 encloses the helical form sample loop h to form a diameter of 4-10cm in the middle part of quality control g.
According to the present invention, in step (II), the gaseous mixture containing hydrogen generated in step (I) is carried to the enrichment
The carrier gas of device is still the first carrier gas described in step (I), is carried out to the gaseous mixture containing hydrogen generated in step (I) rich
The process of collection may include：It sets the mode of communicating of the eight ways valve d to sampling mode of communicating, the sample loop h is put into
In cooling pit, make the gaseous mixture containing hydrogen generated in step (I) under the carrying of the first carrier gas, as shown in Fig. 4 (A), edge
7 path of the 6th the 7th interfaces of interface 6- of second interface 2- third interface 3- sample cells g- is flowed, and is attracted in sample loop h and is filled out
In the duct of the porous material of dress.
According to the present invention, the flow and the flow of the first carrier gas in step (I) of first carrier gas are consistent, still for
80-100mL/min。
According to the present invention, in order to which the foreign gas contained in the gaseous mixture containing hydrogen being enriched in step (II) is removed
Only, and isolated pure hydrogen, the gaseous mixture containing hydrogen being enriched with from step (II) are also needed by gas phase color
It composes column i and carries out further separation, impurity removal.Preferably, in step (III), from the gaseous mixture containing hydrogen being enriched in step (II)
In isolate the process of hydrogen and include：It waits for fluid inclusion water total overall reaction in step (I), no longer generates the mixing containing hydrogen
When gas, the switch knob of rotation eight ways valve d makes the mode of communicating of the eight ways valve d become sample introduction mode of communicating, removes cooling
Trap makes to be adsorbed on the gaseous mixture desorption containing hydrogen in the duct of the porous material loaded in sample loop h, and in the second carrier gas
Carrying under, as shown in Fig. 4 (B), along 4 path of the 6th the 4th interfaces of interface 6- sample cell g- third interface 3- of the 5th interface 5- flow
To gas chromatographic column i, adsorbs and be desorbed through the stationary phase in chromatographic column, hydrogen is detached from gaseous mixture.
According to the present invention, as shown in figure 4, the 5th interface 5 of the eight ways valve d is the air inlet of second carrier gas, when
When the mode of communicating of the eight ways valve d is set as sampling mode of communicating, second carrier gas directly connects along the 5th interface 5- the 6th
The path of mouth 6 flows to gas chromatographic column i；When the mode of communicating of the eight ways valve d becomes sample introduction mode of communicating, described second carries
The gaseous mixture containing hydrogen that gas obtains the porous material desorption out of sample loop h is along the 6th interface 6- samples of the 5th interface 5-
4 path of the 4th interfaces of quality control g- third interface 3- flows to gas chromatographic column i.
According to the present invention, in order to reduce the mixed airflow containing hydrogen being enriched in step (II) through the gas chromatographic column
I and the flow for eventually flowing to the isotope-ratio mass spectrometer make by hydrogen isolated step (III) gas chromatographic column i
Gas enters the isotope-ratio mass spectrometer to the maximum extent, while meeting the isotope-ratio mass spectrometer with higher true
Reciprocal of duty cycle, under preferable case, the flow of second carrier gas is 1-3mL/min.
According to the present invention, there is no particular limitation for the selection of second carrier gas, as long as not influencing porous material in sample loop h
The absorption and separation of material and gas chromatographic column i to the gaseous mixture containing hydrogen being enriched in step (II), and will not be to most
The analysis that whole isotope-ratio mass spectrometer forms hydrogen isotope in fluid inclusion water interferes, it is preferable that described
Second carrier gas is helium.
According to the present invention, finally flowed by the isolated hydrogen of step (III) gas chromatographic column i to further decrease
To the flow of the isotope-ratio mass spectrometer internal ion-source, meet requirement of the ion source to gas flow, to avoid sample introduction
Interference of the gas to ion source, the gas chromatographic column i are preferably connect by open split type with the isotope-ratio mass spectrometer
Mouth j connection settings make to pass through open split type interface j importing isotopic ratio matter through the isolated hydrogen of gas chromatographic column i
Spectrometer.
Had to more subtly adjust the hydrogen flowing quantity for entering the isotope-ratio mass spectrometer according to the present invention
While standby higher throttling function, the airtight of the gas chromatographic column i and the isotope-ratio mass spectrometer junction is ensured
Property is preferably provided with press-fit connector k in the open split type interface j.As shown in figure 5, the press-fit connector k is set
It is placed in one end of the open split type interface j, is fixed side by side in the other end of the open split type interface j and is inserted into second mao
Tubule 2# and third capillary 3#, the fixed outflow end for being inserted into gas chromatographic column i in the arrival end of the press-fit connector k
(the first capillary 1#), and the entrance of the second capillary 2# being inserted into side by side and third capillary 3# and described first mao
The outlet of tubule 1# is oppositely arranged.The third capillary 3# bears the pressure drop of 0.1-0.2MPa, with the isotopic ratio matter
The vacuum pump of spectrometer matches, and the isolated hydrogen of the gas chromatographic column i is directed into the isotopic ratio mass spectrum
The ion source of instrument.The second capillary 2# makes the opening point for being passed through helium into the open split type interface j
Helium is full of in flow pattern interface j.When the flow from hydrogen isolated gas chromatographic column i is more than the isotopic ratio matter
When the working flow of the ion source of spectrometer, excessive gas chromatographic column i outflow hydrogen and second carrier gas are with the second capillary
The helium that 2# is flowed into flows out the open split type interface j；When the flow from hydrogen isolated gas chromatographic column i is less than
When the working flow of the ion source of the isotope-ratio mass spectrometer, the helium in the open split type interface j provides supplement,
And the isolated hydrogen of the gas chromatographic column i is directed into the ion source of the isotope-ratio mass spectrometer.
According to the present invention, under the common adjustment effect of the open split type interface j and the press-fit connector k,
The hydrogen that step (III) is isolated is flowed to the press-fit connection being arranged in open split type interface j by the first capillary 1#
The gas flow of the inlet head k can be 1-3mL/min, and the hydrogen that step (III) is isolated is through in open split type interface j
The gas flow that press-fit connector k is flowed to the ion source of the isotope-ratio mass spectrometer by the third capillary 3# can be with
For 0.3-0.8mL/min, the gas flow for being passed through helium into the open split type interface j from the second capillary 2# can
Think 2-5mL/min.The ion source that this input mode can meet the isotope-ratio mass spectrometer wants gas flow
It asks, and ensures that sample gas enters the ion source of isotope-ratio mass spectrometer to the maximum extent, improve the utilization rate of sample gas,
Realize the analysis of hydrogen isotope in micro fluid inclusion water.
According to the present invention, after sample gas fully enters the ion source of the isotope-ratio mass spectrometer, use is online
It, can be by (being marked according to the world with standard hydrogen when computer analyzes the composition of hydrogen isotope in fluid inclusion water
The hydrogen that accurate or national standard water sample is prepared, and the hydrogen calibration with these standard water samples made from steel cylinder hydrogen)
In1H+With2H+The analysis result of ratio is compared, and detected fluid inclusion water is directly calculated relative to standard water
The δ D values (‰) of the hydrogen isotope composition of sample, and indicate the ratio of corresponding isotope in standard water sample with it, specifically according to
Following formula is calculated：
In formula：SA represents detected fluid inclusion water, and ST represents standard water sample.
The method of hydrogen isotope is simple to operation in on-line analysis fluid inclusion water provided by the present invention, testing efficiency
Height, analysis precision is high, in the case where ensureing the precondition of precision and accuracy, effectively reduces hydrogen isotope in fluid inclusion water
The entire analytic process of amount of samples needed for analysis, each sample can be completed in 5-10 minutes, realize micro fluid
The quick analysis of hydrogen isotope in inclusion water.
The present invention will be described in detail by way of examples below.
In following embodiment, isotope-ratio mass spectrometer is the model Delta S of Thermo Fisher companies production
Isotope-ratio mass spectrometer, the H being prepared by being analysed to fluid inclusion water2Import isotope-ratio mass spectrometer from
Component is detected it, weighs the fluid inclusion of the same race of 6 parts of identical weights and encapsulates sample preparation with tin can or silver cup, and repeats
Analysis 6 times, is averaged as final analysis result.
In following embodiment, using steel cylinder high-purity hydrogen, (δ D values are used as Standard Gases, detected fluid package for -134.1 ‰
The δ D values (‰) of hydrogen isotope indicate that hydrogen isotope forms in detected fluid inclusion water in body water, and with it to Standard Gases
(VSMOW) ratio of corresponding isotope indicates in, is specifically calculated according to the following formula：
In formula, SA represents fluid inclusion water, and VSMOW represents Vienna standard average sea water.
Embodiment 1
(1) by needed for hydrogen isotope in on-line analysis fluid inclusion water each instrument and device assemble
As shown in figure 3, elemental analyser and enriching apparatus, gas chromatographic column i and isotope-ratio mass spectrometer sequence are connected
It connects, wherein the enriching apparatus includes eight ways valve d, sample cell g and the Dewar bottle equipped with liquid nitrogen, the elemental analyser outlet
One end of mouth and gas chromatographic column i are arranged with two orifices of the eight ways valve d respectively, and the gas chromatographic column i's is another
One end is connected to setting with the isotope-ratio mass spectrometer by open split type interface j.
As shown in figure 4, the second interface of the gas vent of the elemental analyser and the eight ways valve d in the enriching apparatus
2 connection settings, the 5th interface 5 and another way carrier gas (helium) sample introduction pipeline connection of the eight ways valve d are arranged, the eight ways valve
The 4th interface 4 of d is connected to setting with the sample introduction end of gas chromatographic column i, and the third interface 3 and the 6th interface 6 of the eight ways valve d divide
Setting is not connected to the both ends of the sample cell g.The internal diameter of the sample cell g is 0.6mm, and the wall thickness of the sample cell g is
0.3mm, the sample loop h are located at the middle part of sample cell g, and the helical form of a diameter of 8cm is formed by 2 circle of winding in the middle part of sample cell g
It is filled with 5A molecular sieves in sample loop h, the sample loop h.
As shown in figure 5, the press-fit connector k to be fixed on to one end of the open split type interface j, the opening
It is fixed side by side in the other end of bypass type interface j to be inserted into the second capillary 2# and third capillary 3#, the press-fit connector k
Arrival end in the fixed outflow end (the first capillary 1#) for being inserted into gas chromatographic column i, and second be inserted into side by side mao
The entrance of tubule 2# and third capillary 3# and the outlet of the first capillary 1# are oppositely arranged.
(2) in fluid inclusion water hydrogen isotope on-line analysis
First, the sample loop h is put into the Dewar bottle equipped with liquid nitrogen, the mode of communicating of the eight ways valve d is arranged
To sample mode of communicating, at this point, as shown in Fig. 4 (A), the second interface 2 of the eight ways valve d is connected to third interface 3, and the 4th connects
Mouth 4 is connected to the 5th interface 5, and the 6th interface 6 is connected to the 7th interface 7, and the 8th interface 8 is connected to first interface 1.
Then, 100mg fluid inclusion samples are weighed, it is packaged using tin can, then the packaged stream
Body inclusion enclave is placed in the solid autosampler f of elemental analyser.It is passed through the first load to being filled in the reaction tube of 50g chromium powders
Gas helium and oxygen, wherein the injection flow of the first carrier gas helium is 80mL/min, and the injection flow of oxygen is 20mL/min,
Reaction tube temperature programming is controlled, when temperature in reaction tube rises to 1000 DEG C, the aforementioned fluid inclusion packaged with tin can is pressed
Program enters through solid autosampler in reaction tube, after note oxygen 30s, closes oxygen and injects valve, stops note oxygen, described to use tin
For the packaged fluid inclusion of cup during noting oxygen, high temperature flash burn, temperature reaches 1800 DEG C, and fluid inclusion is fully quick-fried
It splits, releases the water in Fluid inclusions body.Then, the water of fluid inclusion release at this temperature with the chromium that is loaded in reaction tube
Powder contacts, and reduction reaction occurs, and generates the gaseous mixture containing hydrogen, and under the carrying of first carrier gas helium, flow to eight
Port valve d.And flowed along 7 path of the 6th the 7th interfaces of interface 6- of second interface 2- third interface 3- sample cells g-, and be attracted to
In the duct of the porous material loaded in sample loop h.
Wait for fluid inclusion water total overall reaction, when no longer generating the gaseous mixture containing hydrogen, the switching rotation of rotation eight ways valve d
Button makes the mode of communicating of the eight ways valve d become sample introduction mode of communicating, removes the Dewar bottle equipped with liquid nitrogen, makes to be adsorbed on sample
The gaseous mixture desorption containing hydrogen in the duct of the porous material loaded in ring h, and it is (described under the carrying of the second carrier gas
Second carrier gas is helium, and injection flow is 2mL/min), as shown in Fig. 4 (B), along the 6th interface 6- sample cells g- of the 5th interface 5-
4 path of the 4th interfaces of third interface 3- flows to gas chromatographic column i, through in chromatographic column stationary phase adsorb and desorption, by hydrogen from
It is detached in gaseous mixture.The hydrogen isolated through gas chromatographic column i is flowed to by the first capillary 1# in open split type interface j
The gas flow of the inlet press-fit connector k of setting is 2mL/min, and the hydrogen that step (III) is isolated is through open split
Press-fit connector k in type interface j is flowed to the ion source of the isotope-ratio mass spectrometer by the third capillary 3#
Gas flow is 0.5mL/min, is passed through the gas stream of helium into the open split type interface j from the second capillary 2#
Amount is 4mL/min.
Finally, it is prepared and through hydrogen isolated gas chromatographic column i with aforementioned sample introduction side by the fluid inclusion water
Formula enters the ion source of isotope-ratio mass spectrometer, using on-line computer to the composition of hydrogen isotope in fluid inclusion water into
Row analysis, obtains hydrogen isotope ratio in the hydrogen made from the fluid inclusion water, to obtain wrapping up with detected fluid
Hydrogen isotope ratio in the comparable detected fluid inclusion water of hydrogen isotope ratio in hydrogen made from body water.Analysis result such as table
Shown in 1.The fluid inclusion of the same race of identical weight is weighed, repeats above-mentioned analytic process 6 times, each analysis result such as 2 institute of table
Show.
Embodiment 2
According to embodiment 1 method to needed for hydrogen isotope in on-line analysis fluid inclusion water each instrument and device into
Row assembles and carries out on-line analysis to hydrogen isotope in fluid inclusion water, unlike, during dynamic flash burn, convection current
The material that body inclusion enclave is packaged is silver cup.Analysis result is as shown in table 1.The fluid inclusion of the same race of identical weight is weighed,
Repeat above-mentioned analytic process 6 times, each analysis result is as shown in table 2.
Embodiment 3
According to embodiment 1 method to needed for hydrogen isotope in on-line analysis fluid inclusion water each instrument and device into
Row assembles and carries out on-line analysis to hydrogen isotope in fluid inclusion water, unlike, the internal diameter of the sample cell g is
The wall thickness of 0.5mm, the sample cell g are 0.2mm, and the sample loop h is located at the middle part of sample cell g, by winding in the middle part of sample cell g
2 circles, which are formed in helical form the sample loop h, the sample loop h of a diameter of 5cm, is filled with activated carbon.Analysis result is as shown in table 1.
The fluid inclusion of the same race of identical weight is weighed, repeats above-mentioned analytic process 6 times, each analysis result is as shown in table 2.
Embodiment 4
According to embodiment 1 method to needed for hydrogen isotope in on-line analysis fluid inclusion water each instrument and device into
Row assembles and carries out on-line analysis to hydrogen isotope in fluid inclusion water, unlike, the injection stream of the first carrier gas helium
Amount is 90mL/min, and the injection flow of the second carrier gas helium is 3mL/min.Analysis result is as shown in table 1.Weigh identical weight
Fluid inclusion of the same race, repeats above-mentioned analytic process 6 times, and each analysis result is as shown in table 2.
Embodiment 5
According to embodiment 1 method to needed for hydrogen isotope in on-line analysis fluid inclusion water each instrument and device into
Row assembles and carries out on-line analysis to hydrogen isotope in fluid inclusion water, unlike, it is isolated through gas chromatographic column i
Hydrogen is flowed to the gas stream for the inlet press-fit connector k being arranged in open split type interface j by the first capillary 1#
Amount is 3mL/min, and the hydrogen that step (III) is isolated is through the press-fit connector k in open split type interface j by the third
The gas flow that capillary 3# flows to the ion source of the isotope-ratio mass spectrometer is 0.6mL/min, by second capillary
The gas flow that pipe 2# is passed through helium into the open split type interface j is 3mL/min.Analysis result is as shown in table 1.It weighs
The fluid inclusion of the same race of identical weight, repeats above-mentioned analytic process 6 times, and each analysis result is as shown in table 2.
Comparative example 1
According to embodiment 1 method to needed for hydrogen isotope in on-line analysis fluid inclusion water each instrument and device into
Row assembles and carries out on-line analysis to hydrogen isotope in fluid inclusion water, unlike, gas chromatographic column i and isotope ratio
It is worth mass spectrograph to connect by Conflo type interfaces, and enriching apparatus is wherein not used and bursts the water discharged to fluid inclusion simultaneously
It carries out the gaseous mixture containing hydrogen that reduction reaction obtains to be enriched with, analytical equipment schematic diagram is as shown in Fig. 2, through gas-chromatography
The hydrogen of column i separation is with the flux and flow direction isotope-ratio mass spectrometer of 80mL/min, wherein there is the hydrogen of 72mL/min to be split
Fall, the hydrogen of only residue 8mL/min enters the open split type interface j (open split) of ConFlo, and herein with another way
Helium mix, then a capillary sample gas is imported by ion source by the pressure difference inside and outside ion source, the capillary at this time
Interior gas flow is 0.5mL/min.Fluid inclusion dosage and analysis result are as shown in table 1.Weigh the stream of the same race of identical weight
Body inclusion enclave, repeats above-mentioned analytic process 6 times, and each analysis result is as shown in table 2.
Comparative example 2
Hydrogen isotope in fluid inclusion water is analyzed according to method disclosed in patent of invention CN104181245B,
Fluid inclusion dosage and analysis result are as shown in table 1.The fluid inclusion of the same race of identical weight is weighed, above-mentioned analyzed is repeated
Journey 6 times, each analysis result is as shown in table 2.
Table 1
| Embodiment is numbered | Fluid inclusion dosage | δDSA-VSMOW | Analyze the used time |
| Embodiment 1 | 100mg | -66.1‰ | 7min |
| Embodiment 2 | 100mg | -66.2‰ | 5min |
| Embodiment 3 | 100mg | -66.7‰ | 6min |
| Embodiment 4 | 100mg | -65.8‰ | 9min |
| Embodiment 5 | 100mg | -65.9‰ | 8min |
| Comparative example 1 | 2g | -60.3‰ | 20min |
| Comparative example 2 | 2.5g | -70.2‰ | 120min |
Table 2
Can be seen that by the result of Tables 1 and 2 can improve the same position of solid sample hydrogen using method provided by the invention
Plain test quality makes it suitable for the analysis of hydrogen isotope in micro fluid inclusion water, and can meet mass spectrograph ion
Requirement of the source to gas flow, and the sample gas of generation can be sent into isotope-ratio mass spectrometer to the maximum extent, significantly
The detection of lowering apparatus limits, and under the precondition for ensureing precision, accuracy and reproducibility, effectively reduces fluid inclusion water
Amount of samples needed for middle hydrogen isotope analysis, entire analytic process can be completed in 5-10 minutes, realize micro fluid
The quick analysis of hydrogen isotope in inclusion water.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (15)
1. a kind of method of hydrogen isotope in on-line analysis fluid inclusion water, which is characterized in that the method includes following steps
Suddenly：
(I) in the reaction tube for being filled with chromium powder, so that the water in fluid inclusion is discharged using dynamic flash burn method and aoxidized
Reduction reaction generates the gaseous mixture containing hydrogen；
(II) enriching apparatus is used to be enriched with the gaseous mixture containing hydrogen generated in step (I)；
(III) gas chromatographic column (i) is utilized to isolate hydrogen in the gaseous mixture containing hydrogen of enrichment from step (II)；
(IV) hydrogen for isolating step (III) by open split type interface (j) import isotope-ratio mass spectrometer from
Component carries out the analysis of hydrogen isotope in fluid inclusion water and obtains hydrogen isotope ratio,
Wherein, the enriching apparatus includes eight ways valve (d), sample cell (g) and cooling pit, and the eight ways valve (d), which is provided with, to be used for
The interface of the gaseous mixture containing hydrogen generated in receiving step (I), the mixing containing hydrogen for step (II) to be enriched with
Gas is exported to the interface of gas chromatographic column (i) and the interface for being connected to setting with the both ends of the sample cell (g), and described eight is logical
Valve (d) is additionally provided with switch knob, two kinds of mode of communicating of sampling and sample introduction for switching the eight ways valve (d), the sample
It is provided with helical form sample loop (h) on pipe (g), is filled with porous material in the sample loop (h), the sample loop (h) is with energy
It is freely put into or removal method is arranged in cooling pit, press-fit connector is provided in the open split type interface (j)
(k),
In step (I), the process for making the water in fluid inclusion discharge using dynamic flash burn method includes：Use tin can or silver
Cup is packaged fluid inclusion, and then the packaged fluid inclusion enters reaction tube through solid autosampler
In, the temperature of the reaction tube is controlled to 900-1100 DEG C, in the presence of the first carrier gas, is carried out flash burn, is made fluid inclusion
By thermal spalling, and release the water in fluid inclusion.
2. according to the method described in claim 1, wherein, in step (I), first carrier gas is with the flow of 80-100mL/min
Inject reaction tube.
3. according to the method described in claim 1, wherein, in step (I), the process of the dynamic flash burn is under conditions of noting oxygen
It carries out.
4. according to the method described in claim 3, wherein, the condition of the note oxygen includes：Note oxygen flow is 15-30mL/min,
The note oxygen time is 20-60s, and flash ignition temperature reaches 1700-1800 DEG C.
5. according to the method described in claim 1, wherein, in step (I), the process of the redox reaction includes：Adding
Under conditions of heat, the water that fluid inclusion discharges is made to be contacted with the chromium powder loaded in reaction tube.
6. according to the method described in claim 5, wherein, the condition of the heating includes：Heating temperature is 900-1100 DEG C, is added
The hot time is 5-12min.
7. according to the method described in claim 5, wherein, the weight of the amount of fill of the chromium powder and the dosage of the fluid inclusion
Amount is than being 500-1500：1.
8. according to the method described in claim 1, wherein, the cooling pit is the Dewar bottle equipped with coolant.
9. according to the method described in claim 8, wherein, the coolant is liquid nitrogen.
10. according to the method described in claim 1, wherein, the internal diameter of the sample cell (g) is 0.4-0.8mm, wall thickness 0.2-
0.5mm, the sample loop (h) are located at the middle part of sample cell (g), are enclosed by winding 1-3 in the middle part of sample cell (g) and form a diameter of 4-
The helical form sample loop (h) of 10cm.
11. according to the method described in claim 1, wherein, the eight ways valve (d) is provided with first interface (1)~the 8th interface
(8), each interface interface adjacent thereto selects a connection, when the eight ways valve (d) is connected in a manner of sampling or sample introduction respectively,
The connected relation of each interface of the eight ways valve (d) is respectively：
When the mode of communicating of the eight ways valve (d) is sampling mode of communicating, second interface (2) is connected to third interface (3), the
Four interfaces (4) are connected to the 5th interface (5), and the 6th interface (6) is connected to the 7th interface (7), the 8th interface (8) and first interface
(1) it is connected to；
When the mode of communicating of the eight ways valve (d) is sample introduction mode of communicating, second interface (2) is connected to first interface (1), the
Four interfaces (4) are connected to third interface (3), and the 6th interface (6) is connected to the 5th interface (5), the 8th interface (8) and the 7th interface
(7) it is connected to.
12. method according to claim 1 or claim 7, wherein in step (II), to what is generated in step (I) containing hydrogen
The process that gaseous mixture is enriched with includes：The mode of communicating of the eight ways valve (d) is set to sampling mode of communicating, by the sample
Product ring (h) is put into cooling pit, makes the gaseous mixture containing hydrogen generated in step (I) under the carrying of the first carrier gas, along the
Two interfaces (2)-six interface of third interface (3)-sample cell (g)-the (6)-the seven interface (7) path flowing, and it is attracted to dress
Have in the sample loop (h) of porous material.
13. method according to claim 1 or claim 7, wherein in step (III), contain hydrogen from what is be enriched in step (II)
Gaseous mixture in isolate the process of hydrogen and include：When step (I) no longer generates the gaseous mixture containing hydrogen, eight ways valve is rotated
(d) switch knob makes the mode of communicating of the eight ways valve (d) become sample introduction mode of communicating, removes cooling pit, makes to be adsorbed on dress
There is the gaseous mixture desorption containing hydrogen in the sample loop (h) of porous material, and under the carrying of the second carrier gas, along the 5th interface
(5)-the six interfaces (6)-sample cell (g)-third interface (3)-the four interface (4) path flows to gas chromatographic column, through gas phase color
Stationary phase absorption and the desorption in column are composed, hydrogen is detached from gaseous mixture.
14. according to the method for claim 13, wherein the flow of second carrier gas is 1-3mL/min.
15. according to the method described in claim 1, wherein, in step (IV), the hydrogen that step (III) is isolated passes through opening
During bypass type interface (j) imports the ion source of isotope-ratio mass spectrometer, the hydrogen that step (III) is isolated flows through out
The flow of mouth inlet bypass type interface (j) is 1-3mL/min, and the hydrogen that step (III) is isolated is through open split type interface
(j) flow that the press-fit connector (k) in flows to the ion source of the isotope-ratio mass spectrometer is 0.3-0.8mL/min.
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| CN108844801A (en) * | 2018-09-13 | 2018-11-20 | 中国地质科学院矿产资源研究所 | Fluid inclusion carbon and hydrogen isotope analysis system and method for minerals difficult to thermally decompose |
| CN109060932A (en) * | 2018-09-13 | 2018-12-21 | 中国地质科学院矿产资源研究所 | Carbon and hydrogen isotope analysis system and method for mineral fluid inclusion |
| CN109100413A (en) * | 2018-09-13 | 2018-12-28 | 中国地质科学院矿产资源研究所 | System and method for analyzing carbon and hydrogen isotopes oil-free valve of mineral fluid inclusion |
| GB2588760B (en) * | 2019-10-30 | 2022-06-22 | Thermo Fisher Scient Bremen Gmbh | Interface system and corresponding method |
| CN111272917A (en) * | 2020-03-30 | 2020-06-12 | 中国科学院地质与地球物理研究所 | Element isotope analysis system and method for analyzing sulfur isotope in trace sulfate sample and application thereof |
| CN115326962B (en) * | 2022-08-15 | 2024-04-02 | 中国科学院西北生态环境资源研究院 | Hydrogen isotope determination device and method for hydrogen sulfide in natural gas |
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