CN101907618B - Generator capable of generating water vapor with constant hydrogen and oxygen stable isotope ratio and application - Google Patents
Generator capable of generating water vapor with constant hydrogen and oxygen stable isotope ratio and application Download PDFInfo
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- CN101907618B CN101907618B CN 201010223551 CN201010223551A CN101907618B CN 101907618 B CN101907618 B CN 101907618B CN 201010223551 CN201010223551 CN 201010223551 CN 201010223551 A CN201010223551 A CN 201010223551A CN 101907618 B CN101907618 B CN 101907618B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 19
- 239000001301 oxygen Substances 0.000 title claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 18
- 239000001257 hydrogen Substances 0.000 title claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 230000008020 evaporation Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims abstract description 6
- 239000007924 injection Substances 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- 230000000155 isotopic effect Effects 0.000 claims description 21
- 238000011049 filling Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- 238000013459 approach Methods 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 210000004907 gland Anatomy 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
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Abstract
本发明提供了一种可以根据需要产生不同浓度的具有恒定氢氧稳定同位素比值的水汽发生器及方法。可以用于大气水汽稳定同位素仪器的标定，实现仪器的连续或定期的性能评价或标定或者可以直接用于不同浓度水汽的发生器，便于在野外安装和拆卸。本发明包括包括六个部分：(1)微量滴水装置；(2)蒸发装置；(3)恒温加热装置；(4)干空气注入装置；(5)水汽出口；(6)空气混合装置。
The invention provides a water vapor generator and a method that can produce different concentrations according to requirements and have a constant hydrogen-oxygen stable isotope ratio. It can be used for the calibration of atmospheric water vapor stable isotope instruments to achieve continuous or regular performance evaluation or calibration of the instrument, or it can be directly used for generators of different concentrations of water vapor, which is convenient for installation and disassembly in the field. The invention includes six parts: (1) micro dripping device; (2) evaporation device; (3) constant temperature heating device; (4) dry air injection device; (5) water vapor outlet; (6) air mixing device.
Description
Technical field:
It is ecological to the present invention relates to aerology, hydrology and stable isotope, especially relates to the calibration technique of atmosphere vapour stable isotope instrument.
Background technology:
Since the existence of isotope effect, H
2 18O, HD
16O and H
2 16O has become the best tracer agent of multi-form moisture movement between soil, vegetation, atmosphere and ocean, has become multi-disciplinary research instruments such as relating to atmosphere, the hydrology and ecology.Because very high in the relative abundance of occurring in nature light isotope, and the relative abundance of heavy isotope is very low, so isotopic ratio adopts the δ value to represent usually,
δ＝(R/R
Std-1)×1000‰ (1)
Wherein R is
18O/
16O or D/H mol ratio, R
StdIt is standard substance
18O/
16O or D/H mol ratio adopt the average seawater of Vienna (Vienna) standard (V-SMOW), wherein at present usually
18O/
16O is 0.0020052, and D/H is 0.00015576.The unit of the isotopic ratio of representing with the δ form is per mille (‰).
To gaseous state, liquid state and solid water δ
18Measure in the time of O and δ D the important information that discloses atmospheric water source region and phase transition process can be provided.With liquid and solid water δ
18O compares with the observation of δ D, to steam δ
18The observation of O and δ D can be carried out under Various Seasonal and weather condition, and is not limited to the weather condition of precipitation or snowfall generation, thereby the liquid and solid water δ than simple utilization can be provided
18O and δ D data are more about the information of aspects such as aerology, hydrology and stable isotope ecology.
Atmosphere vapour δ in the past
18O and δ D research nearly all relies on atmosphere vapour cold-trap/isotope mass spectrometer technology (cold-trap/mass spectrometer method), all comprise two steps usually: sample collection and sample analysis, and these two steps all are unusual time and effort consumings.Particularly the work period of sample collection is relevant with the vapour concentration of atmosphere itself; Under relatively drier atmospheric conditions; The sample collecting time often needs the longer time; Thereby the signal that causes during this, changing originally is by the collection of distortion, and the comparability between the sample possibly produce secondary error owing to the difference of acquisition time.In recent years, (Tunable Diode Laser Absorption Spectroscopy, TDLAS) development of technology makes to atmosphere vapour δ the modulation system semi-conductor laser absorption spectrum
18The original position Continuous Observation of O and δ D becomes possibility.After the TDLAS technology; From axle integration chamber output spectrum (Ofi-Axis Integrated Cavity Output Spectroscopy; OA-ICOS) and the wavelength scanning light cavity ring-down spectroscopy (Wavelength-Scanned Cavity Ring Down Spectroscopy, WS-CRDS) development of technology also makes to atmosphere vapour δ
18The Continuous Observation of O and δ D becomes possibility.But, atmosphere vapour δ
18The influence that the accuracy of observation of O and δ D stable isotope observation instrument is changed by external environmental condition and LASER Light Source self has tangible nonlinear response problem usually.What the nonlinear response of instrument referred to Instrument observation has a constant hydrogen and oxygen stable isotopic ratio (δ
18O and δ D) the steam result of variable concentrations should have identical δ
18O and δ D, but showing as different numerical is nonlinear response characteristic.Therefore, need to adopt suitable calibration facility and method to demarcate, observed result could be used.
Therefore, can produce fast and accurately and can follow two concentration between the upper and lower region that natural atmosphere changes, and steam generator and method with constant hydrogen and oxygen stable isotopic ratio are to realize atmosphere vapour δ
18The demarcation that O and δ D stable isotope observation instrument are continuous or periodic is also obtained the prerequisite of quality data.Traditional atmosphere vapour cold-trap/mass spectrometry art is not suitable for the performance evaluation or the demarcation of system under the open-air in-situ observation condition.Mainly contain following three reasons: the first, atmosphere vapour cold-trap/mass spectrometry art time and effort consuming; The second, be subject to the influence of cold-trap error that condensation efficiency causes; The 3rd, also be most important, the result of the steam sample that is collected just can obtain after can only waiting until spectrometer analysis, and this is very unpractical for open-air original position Continuous Observation test.This will make the performance of original position spread for continuous profiling guarantee technically.
Summary of the invention:
For overcoming atmosphere vapour δ
18The nonlinear response problem of O and δ D stable isotope observation instrument; Overcome traditional atmosphere vapour cold-trap/mass spectrometry art and be not suitable for the performance evaluation of instrument under the open-air in-situ observation condition or the shortcoming of demarcation; Developed a kind of steam generator and purposes that has the constant hydrogen and oxygen stable isotopic ratio and can follow two variable concentrations of natural atmosphere variation; Can be used for the continuous or periodic performance evaluation or the demarcation of atmosphere vapour stable isotope instrument, perhaps can directly be used for the generator of continuous vapour concentration.
Technical scheme of the present invention is:
A kind of steam generator of constant hydrogen and oxygen stable isotopic ratio comprises following six parts:
1) micro-dripping device comprises aqueous water container (11) and two-way or unidirectional micro-water filling device (15);
2) vaporising device comprises evaporative flask (21), seal bottle cap (22) and auxiliary seal equipment (23) and (24);
3) heating arrangement comprises well heater (31) and warming plate (32);
4) dry air injection device comprises accurate flow controller (41), the molecular sieve that dewaters (42), three-way interface (44) and needle-valve (45);
5) steam of constant hydrogen and oxygen stable isotopic ratio outlet comprises four-way interface (52), accurate flow controller (53) and (55) and three-way interface (54);
6) air mixing device comprises fan (61).
Adorn the liquid water of known stable isotope ratio in the described aqueous water container (11); Through two-way or unidirectional micro-water filling device (15), cooperate carrying out flash evapn on the evaporation piece (17) in the aqueous water injection evaporative flask (21) of known stable isotope ratio with two three-way solenoid valves (14).
Described evaporative flask (21) utilizes seal bottle cap (22) sealing, and four sealable interface channels are arranged on the seal bottle cap, and evaporative flask (21) utilizes auxiliary sealing device (23) and (24) to carry out auxiliary seal after covering gland bonnet (22) again; Evaporative flask (21) after the sealing is placed on the well heater (31), and utilizes warming plate (32) that the evaporative flask (21) of sealing is heated and is incubated.
Described dry air is through behind the accurate flow controller (41); Pass through three-way interface (44) process sealed interface (25) through molecular sieve (42) back that dewaters and get into evaporative flask (21), the anhydrous dry air of part advances to use through the steam that three-way interface (44) utilizes needle-valve (45) shunting to offer back generation mixing; Utilize exhaust fan (61) that evaporation steam and dry air in the evaporative flask (21) are fully mixed, promptly obtain to have the vaporous water of known stable isotope ratio; The steam of known stable isotope ratio is supplied with accurate flow controller (53) and (55) simultaneously through four-way interface (52), and three path of unnecessary steam through four-way interface (52) enters atmosphere; The steam that flows through accurate flow controller (53) is the target approach instrument directly; Flow through the steam of accurate flow controller (55) with through three-way interface (54) thus a small amount of dry air further mixes the reduction vapour concentration but still has the steam gas of constant stable isotope ratio, direct target approach instrument.
Described aqueous water container (11) is glass or polytetrafluoroethylcontainer container.Evaporative flask (21) is a vial, and seal bottle cap (22) is the teflon material.Well heater (31) can continue heating, maintains the temperature between 95～100 ℃.Dry air injects accurate flow controller of flow utilization (41) and needle-valve (45) control; Mix the back steam accurate flow controller of flow utilization (53) and (55) control.It all is to utilize polyfluortetraethylene pipe to connect that all pipelines that passes through steam connect.
The purposes of above-mentioned steam generator in the demarcation of the atmosphere vapour isotope of variable concentrations and atmosphere vapour stable isotope instrument with constant hydrogen and oxygen stable isotopic ratio.
Technique effect:
Be convenient to install in the open air, dismantle, can produce the steam with constant hydrogen and oxygen stable isotopic ratio of variable concentrations as required, be used for the demarcation of atmosphere vapour stable isotope instrument, realize the continuous or periodic demarcation of instrument.Confirm and define a kind of suitable field condition, can be independently and timely this original position spread for continuous profiling performance is carried out the method for objective evaluation.
Description of drawings:
Fig. 1 is the assembling synoptic diagram of the steam generator of constant hydrogen and oxygen stable isotopic ratio.
Embodiment:
Below describe and only represent a kind of embodiment of the present invention,, rather than limit the invention just for further the present invention will be described.
The steam generator of constant hydrogen and oxygen stable isotopic ratio comprises six parts: first: micro-dripping device mainly comprises aqueous water container (11) and two-way or unidirectional micro-water filling device (15); Second: vaporising device mainly comprises evaporative flask (21), seal bottle cap (22) and auxiliary seal equipment (23) and (24); The 3rd: heating arrangement mainly comprises constent temperature heater (31) and warming plate (32); The 4th: the dry air injection device mainly comprises accurate flow controller (41), the molecular sieve that dewaters (42), three-way interface (44) and needle-valve (45); The 5th: the steam outlet of constant hydrogen and oxygen stable isotopic ratio mainly comprises four-way interface (52), accurate flow controller (53) and (55) and three-way interface (54); The 6th: air mixing device mainly comprises fan (61).
Adorn known stable isotope ratio in the aqueous water container (11) (like δ
18O be-10.00 ‰ with δ D for-100.0 ‰) liquid water; Through two-way or unidirectional micro-water filling device (15) (PHD2000; Harvard apparatus inc.), cooperate with two three-way solenoid valves (14) carrying out flash evapn on the evaporator (17) in the aqueous water injection evaporative flask (21) of known stable isotope ratio; Evaporative flask (21) utilizes seal bottle cap (22) sealing, and four sealable interface channels are arranged on the seal bottle cap, and evaporative flask (21) utilizes auxiliary sealing device (23) and (24) to carry out auxiliary seal after covering gland bonnet (22) again; Evaporative flask (21) after the sealing is placed on the well heater (31), and utilizes warming plate (32) that the evaporative flask (21) of sealing is heated and is incubated; (FMA 5400/5500 through accurate flow controller 41 for anhydrous dry air; Omega) after; Get into evaporative flask (21) through passing through three-way interface (44) behind the molecular sieve (42) that dewaters through sealed interface (25), the anhydrous dry air of part further mixes use through the steam that three-way interface (44) utilizes needle-valve (45) Control Flow to offer back mixing generation; Utilize exhaust fan (61) that evaporation steam and dry air in the evaporative flask (21) are fully mixed, promptly obtain to have known stable isotope ratio (like δ
18O be-10.00 ‰ with δ D for-100.0 ‰) vaporous water; Through two accurate flow controllers (53) and (55) (FMA 5400/5500, Omega inc.), unnecessary steam enters atmosphere through four-way interface (52) to the steam of known stable isotope ratio through four-way interface (52).The steam that flows through accurate flow controller (53) is the target approach instrument directly; Flow through the steam of accurate flow controller (55) with through three-way interface (54) thus a small amount of dry air further mixes the reduction vapour concentration but still has the steam gas of constant stable isotope ratio, direct target approach instrument.
Adorn known stable isotope ratio in the aqueous water container (11) (like δ
18O be-10.00 ‰ with δ D for-100.0 ‰) liquid water.The outflow of the aqueous water in a two-way valve (13) the control aqueous water container (11) is installed in the bottom of aqueous water container (11).The bottom was a little more than two-way or unidirectional micro-water filling device (15), so that aqueous water (12) can flow out through two-way valve (13) through the effect of action of gravity when aqueous water container (11) was installed., cooperate to micro-water filling device (15) through two-way (or single), the aqueous water of known stable isotope ratio is gone up the evaporation piece (17) that injects in the evaporative flask (21) sealable interface channel through seal bottle cap (22) evaporate with two three-way solenoid valves (14).All connections all utilize pipeline (16) to connect.
Evaporative flask (21) utilizes seal bottle cap (22) sealing, and four sealable interface channels are arranged on the seal bottle cap.Four sealable interface channels are respectively applied for the import of fan power supply line, dry air import, aqueous water import and mixed water vapor outlet.Evaporative flask (21) utilizes auxiliary sealing device (23) and (24) to seal after covering gland bonnet (22) again.Packoff (23) is the metal plates of two areas greater than evaporative flask (21) bottom, a metal plate that leaves four circular holes that can be complementary with four sealed interfaces (25) of seal bottle cap (22), and other one is complete metal plate.With four long screws (24) and up and down two metal plates (23) will utilize the evaporative flask (21) of seal bottle cap (22) sealing further to compress sealing.
Evaporative flask (21) after the sealing is placed on the dull and stereotyped constent temperature heater (31).Well heater (31) can continue heating, guarantees to splash into the steam flash evapn of evaporative flask.Utilize four warming plates (32) that evaporative flask (21) sealing is incubated.Utilize the junction of material seal warming plates (32) such as soft cloth and metal plate (32) to be incubated.
Utilize accurate flow controller (41) control to get into the flow of the anhydrous dry air of evaporative flask (21).After anhydrous dry air need pass through the molecular sieve that dewaters (42) and further dewaters, the back got into evaporative flask (21) through three-way interface (44) through sealed interface (25).The anhydrous dry air that gets into evaporative flask (21) is directly annotated the bottom of evaporative flask (21).The anhydrous dry air of part further mixes use through the steam that three-way interface (44) utilizes needle-valve (45) Control Flow to offer back mixing generation.All connections all utilize pipeline (43) to connect.
With the fixing bottom of evaporative flask (21) of exhaust fan (61), and near the bottle wall.Utilizing power lead (62) to go up sealable interface channel through seal bottle cap (22) gets in the evaporative flask (21) to exhaust fan (61) power supply.Utilize exhaust fan (61) that evaporation steam and dry air in the evaporative flask (21) are fully mixed, obtain to have known stable isotope ratio (like δ
18O be-10.00 ‰ with δ D for-100.0 ‰) vaporous water.
The steam of the known stable isotope ratio that the interior exhaust fan of evaporative flask (21) (61) mixes utilizes accurate flow controller (53) and (55) control to get into the steam flow through passing through two accurate flow controllers (53) and (55) behind the four-way interface (52) respectively.The steam that flows through accurate flow controller (53) is the target approach instrument directly.Flow through the steam of accurate flow controller (55) with through three-way interface (54) thus a small amount of dry air further mixes the reduction vapour concentration but still has the steam gas of constant stable isotope ratio, direct target approach instrument.The flow of anhydrous dry air entering evaporative flask (21) will be obviously greater than the steam flow through accurate flow controller (53) and (55).All connections all utilize pipeline (51) to connect.Unnecessary steam can enter atmosphere through four-way interface (52).Perhaps, can to get into other target instrument be to demarcate when realizing a plurality of instrument or further mixes with a small amount of anhydrous dry air to produce vapour concentration gradient gas or get into the vapour concentration analyser and monitor vapour concentration for unnecessary steam.
The present invention further provides a kind of purposes of steam generator of constant hydrogen and oxygen stable isotopic ratio:
Adorn known stable isotope ratio in the aqueous water container (11) (like δ
18O be-10.00 ‰ with δ D for-100.0 ‰) liquid water (12).The outflow of the aqueous water in a two-way valve (13) the control aqueous water container is installed in the bottom of aqueous water container (11).The aqueous water container should keep partial state airtight guaranteeing and atmosphere keeps faint being communicated with, thereby guarantees that the isotope fractionation that aqueous water evaporation in a short time causes can ignore.Can guarantee simultaneously that aqueous water in the container flows can not produce negative pressure and keep malleation, so that the effect that aqueous water can be through action of gravity is through two-way valve (13) outflow.The bottom was a little more than two-way or unidirectional micro-water filling device (15) when aqueous water container (11) was installed.Utilize two-way micro-water filling device (15) to cooperate and to realize continuous micro-water filling with three-way solenoid valve (14).Through two-way or unidirectional micro-water filling device (15) with 1～14 μ L min
-1Speed the aqueous water of known stable isotope ratio is injected the evaporation piece (17) in the evaporative flask (21) through sealable interface channel (22) on the seal bottle cap.Aqueous water in the evaporative flask (21) will become vaporous water by flash evapn, and therefore, vaporous water has identical stable isotope ratio with aqueous water.
Evaporative flask (21) utilizes seal bottle cap (22) sealing, and four sealable interface channels (25) are arranged on the seal bottle cap (22).Four sealable interface channels (25) are respectively applied for the import of fan power supply line, dry air import, mixed water vapor outlet and aqueous water import.Evaporative flask (21) covers and utilizes auxiliary sealing device (23,24) again behind the gland bonnet (22) and seal.Packoff (23) is two areas greater than the metal plates (23) of evaporative flask bottom, and one is to leave the be complementary metal plate of circular hole of four four sealable interface channels (25) with seal bottle cap (22), and other one is exactly metal plate.With four special long screws (24) and up and down two metal plates (23) will utilize the evaporative flask (21) of seal bottle cap (22) sealing further to compress sealing.During all installations, can seal three in four sealable interface channels, utilize another one to connect gas cylinder, air pressure is closed gas cylinder after reaching 20psi, and whether whether testing fixture leaks gas can be safeguarded that promptly air pressure is constant.
Evaporative flask (21) after the sealing is placed on the dull and stereotyped constent temperature heater (31).Well heater (31) can continue heating, maintains the temperature at a certain steady temperature between 95～100 ℃, guarantees to splash into the steam flash evapn of evaporative flask (21).Utilize four warming plates (24) that evaporative flask (21) is incubated.Utilize materials such as soft cloth that pipeline and evaporative flask (21) binding site are carried out covering and heat insulating simultaneously.Can locate to install the actual temperature of two thermocouple monitoring evaporative flasks (21) in bottle cap (22) with bottle bottom.
Utilize accurate flow controller (41) control to get into the flow of 99.999% anhydrous dry air of evaporative flask (21).Flow should remain on 300～2000ml min greater than the marked gas flow of the entering instrument of setting
-3In the scope.After anhydrous dry air need pass through the molecular sieve that dewaters (42) and further dewaters, the back got into evaporative flask (21) through three-way interface (44) through sealed interface (22).The anhydrous dry air that gets into evaporative flask (21) is directly annotated the bottom of evaporative flask (21).The anhydrous dry air of part further mixes use through the steam that three-way interface (44) utilizes needle-valve control (45) system flow to offer back mixing generation.
With the fixing bottom of evaporative flask (21) of exhaust fan (61), and near the bottle wall.Utilizing power lead (62) to go up sealable interface channel (25) through seal bottle cap (22) gets in the evaporative flask (21) to exhaust fan (61) power supply.Utilize exhaust fan (61) that evaporation steam and dry air in the evaporative flask (21) are fully mixed, obtain to have known stable coordination ratio (like δ
18O be-10.00 ‰ with δ D for-100.0 ‰) vaporous water.
Utilize the steam of the known stable isotope ratio of exhaust fan (61) mixing to pass through to pass through two accurate flow controllers (53,55) respectively behind the four-way interface (52) in the evaporative flask (21), utilize accurate flow controller control (53,55) to get into the steam flow.Here be example with the standard correction gas (S1 and S2) that produces two spans.Quantitative dry air gets into evaporative flask (21) to be mixed with the steam of quantitative aqueous water evaporation, and the soft air of generation is calibrating gas S2 after mixing, advise its vapor-to-liquid ratio will be higher than Instrument observation the atmosphere vapour mixing ratio about 5%.Steam S2 concentration can be regulated according to the liquid water yield and dry air amount, produces the steam of variable concentrations.The steam S2 that flows through accurate flow controller (53) is the target approach instrument directly.
Flow through the steam of accurate flow controller (55) with through three-way interface (54) thus a small amount of dry air further mixes the reduction vapour concentration but still has the steam gas S1 of constant stable isotope ratio, advise that its vapor-to-liquid ratio will be lower than about 5% of atmosphere vapour mixing ratio.Steam S1 is direct target approach instrument also.The flow of anhydrous dry air entering evaporative flask (21) will be obviously greater than the steam flow through accurate flow controller (53,55).Unnecessary steam can enter atmosphere through four-way interface (52).Perhaps, can to get into other target instrument be to demarcate when realizing a plurality of instrument or further mixes with a small amount of anhydrous dry air to produce vapour concentration gradient gas or get into the vapour concentration analyser and monitor vapour concentration for unnecessary steam.
All connections through steam all utilize teflon (Polytetrafluoroethene is called for short Teflon) pipeline to connect.Polyfluortetraethylene pipe is to H2
18O, HD
16O and H2
16O does not have suction-operated, promptly can not cause the generation of isotope fractionation effect.
Atmosphere vapour δ
18The computing method that O and δ D demarcate: because the flash evapn of aqueous water in the evaporative flask, calibrating gas S2 has identical isotopic ratio (δ with S1 with the aqueous water of the pump that drips so
18O be-10.00 ‰ with δ D for-100.0 ‰).Utilize the demarcation gas (S2 and S1) of two humidity spans of steam generator generation of constant hydrogen and oxygen stable isotopic ratio to follow the tracks of the variation of ambient atmosphere vapour concentration.Zero calibration can directly utilize through 99.999% dry air of molecular sieve and directly supply with.
As previously mentioned, atmosphere vapour δ
18Therefore the influence that the accuracy of observation of O and δ D stable isotope observation instrument is changed by external environmental condition and LASER Light Source self can't confirm δ exactly
18The true value of O and δ D.Gas S1, S2 and zero gas that desirability utilizes the steam generator of constant hydrogen and oxygen stable isotopic ratio to produce carry out on-line proving, observation data is proofreaied and correct can obtain atmosphere vapour δ
18The true value of O and δ D.
Atmosphere vapour δ
18The correction of O and δ D is divided into two steps.Suppose x
iBe the uncorrected steam mole mixture ratio of i air intake opening of this system (i=1,2,3,4, be respectively S1, S2, zero gas and ambient atmosphere), and
Be uncorrected minimum gas (H
2 18O or HDO) mole mixture ratio (i=1,2,3,4, be respectively S1, S2, zero gas and ambient atmosphere).
Therefore, if S1 when the calibrating gas, atmosphere vapour δ
18O or δ D can be expressed as
When perhaps S2 is as calibrating gas, atmosphere vapour δ
18O or δ D also can be expressed as,
Here R
dBe the liquid water of proofreading and correct in the aqueous water container
18O/
16The molar ratio of O or D/H.Result after the correction can convert the δ symbolic representation into,
δ
1＝(R
1/R?
Std-1)×1000‰ (3a)
With
δ
2＝(R
2/R?
Std-1)×1000‰ (3b)
R wherein
1And R
2Be
18O/
16O or D/H mol ratio, R
StdIt is standard substance
18O/
16O or D/H mol ratio adopt the average seawater of Vienna (Vienna) standard (V-SMOW), wherein at present usually
18O/
16O is 0.0020052, and D/H is 0.00015576.The unit of the isotopic ratio of representing with the δ form is per mille (‰).
For further reducing atmosphere vapour δ
18The nonlinearity erron of O and δ D stable isotope observation instrument utilizes δ
1And δ
2Carry out linear interpolation and obtain real atmosphere vapour δ
18O or δ D,
Claims (10)
1. the steam generator of a constant hydrogen and oxygen stable isotopic ratio is characterized in that comprising following six parts:
1) micro-dripping device comprises aqueous water container (11), two-way or unidirectional micro-water filling device (15) and evaporation piece (17);
2) vaporising device comprises evaporative flask (21), seal bottle cap (22) and auxiliary seal equipment (23) and (24);
3) heating arrangement comprises well heater (31) and warming plate (32);
4) dry air injection device comprises accurate flow controller (41), the molecular sieve that dewaters (42), three-way interface (44) and needle-valve (45);
5) steam of constant hydrogen and oxygen stable isotopic ratio outlet comprises four-way interface (52), accurate flow controller (53) and (55) and three-way interface (54);
6) air mixing device comprises fan (61).
2. steam generator as claimed in claim 1 is characterized in that:
Adorn the liquid water of known stable isotope ratio in the described aqueous water container (11); Through two-way or unidirectional micro-water filling device (15), cooperate aqueous water with known stable isotope ratio to inject continuously on the evaporation piece (17) in the evaporative flask (21) with two three-way solenoid valves (14) and carry out flash evapn.
3. steam generator as claimed in claim 2 is characterized in that:
Described evaporative flask (21) utilizes seal bottle cap (22) sealing, and four sealable interface channels are arranged on the seal bottle cap, and evaporative flask (21) utilizes auxiliary sealing device (23) and (24) to carry out auxiliary seal after covering gland bonnet (22) again; Evaporative flask (21) after the sealing is placed on the well heater (31), and utilizes warming plate (32) that the evaporative flask (21) of sealing is heated and is incubated.
4. steam generator as claimed in claim 3 is characterized in that:
Described dry air is through behind the accurate flow controller (41); Through passing through three-way interface (44) process sealed interface (25) entering evaporative flask (21) behind the molecular sieve (42) that dewaters, the anhydrous dry air of part utilizes needle-valve (45) to regulate and shunt the steam that offers generation mixing at the back through three-way interface (44) and uses; Utilize exhaust fan (61) that evaporation steam and dry air in the evaporative flask (21) are fully mixed, promptly obtain to have the vaporous water of known stable isotope ratio; The steam of known stable isotope ratio is supplied with accurate flow controller (53) and (55) simultaneously through four-way interface (52), and three path of unnecessary steam through four-way interface (52) enters atmosphere; Flow through the direct target approach instrument of steam of accurate flow controller (53); Flow through the steam of accurate flow controller (55) with through three-way interface (54) thus a small amount of dry air further mixes the steam gas that reduces vapour concentration but still have constant stable isotope ratio, direct target approach instrument.
5. like the arbitrary described steam generator of claim 1-4, it is characterized in that: described aqueous water container (11) is glass or polytetrafluoroethylcontainer container.
6. like the arbitrary described steam generator of claim 1-4, it is characterized in that: described evaporative flask (21) is a vial, and seal bottle cap (22) is the teflon material.
7. like the arbitrary described steam generator of claim 1-4, it is characterized in that: described well heater (31) continues heating, maintains the temperature between 95～100 ℃.
8. like the arbitrary described steam generator of claim 1-4, it is characterized in that: dry air injects accurate flow controller of flow utilization (41) and needle-valve (45) control; Mix the back steam accurate flow controller of flow utilization (53) and (55) control.
9. like the arbitrary described steam generator of claim 1-4, it is characterized in that: it all is to utilize polyfluortetraethylene pipe to connect that all pipelines that passes through steam connect.
10. like the purposes of the arbitrary described steam generator of claim 1-9 in the demarcation of the atmosphere vapour isotope of variable concentrations and atmosphere vapour stable isotope instrument with constant hydrogen and oxygen stable isotopic ratio.
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| CN102621276B (en) * | 2012-03-09 | 2014-12-03 | 中国科学院寒区旱区环境与工程研究所 | Device capable of controllably correcting ratio, gradient and vertical fractional distillation process measurement of oxyhydrogen stable isotope in atmospheric water |
| CN106198405B (en) * | 2016-07-04 | 2020-03-13 | 中国气象科学研究院 | System for monitoring hydrogen-oxygen stable isotope ratio of atmospheric water vapor |
| CN106483079A (en) * | 2016-09-23 | 2017-03-08 | 中国气象科学研究院 | The treating method and apparatus of the measurement data of hydrogen and oxygen stable isotope ratio in steam |
| CN108801735A (en) * | 2018-06-26 | 2018-11-13 | 深圳雨伦环境科技有限公司 | A kind of plant leaf blade water isotope enrichment signal tagging system and labeling method |
| CN109459396B (en) * | 2018-12-04 | 2023-08-25 | 南京信息工程大学 | Online laser detection analyzer for carbon isotopes of atmospheric particulates and application method thereof |
| CN111443162B (en) * | 2020-03-06 | 2021-09-17 | 河海大学 | Hydrogen-oxygen isotope fractionation experimental device for teaching and use method |
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