CN109540621B - The method of the extraction system and water oxygen isotope analysis of water oxygen isotope - Google Patents
The method of the extraction system and water oxygen isotope analysis of water oxygen isotope Download PDFInfo
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- VTVVPPOHYJJIJR-UHFFFAOYSA-N carbon dioxide;hydrate Chemical compound O.O=C=O VTVVPPOHYJJIJR-UHFFFAOYSA-N 0.000 claims description 58
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
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- Physics & Mathematics (AREA)
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- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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Abstract
The present invention relates to isotope analysis technical fields, disclose a kind of extraction system for analyzing water oxygen isotope and the method for carrying out water oxygen isotope analysis using the extraction system.The extraction system includes balancing unit, sample collection unit and vacuum unit, wherein, the balancing unit is connected to sample collection unit to be arranged and is sequentially ingressed into vacuum unit, it include multiple balancers in the balancing unit, the sample collection unit includes multiple sample collection tubes, the extraction system integrates balancing unit and sample collection unit well, simplify experimental implementation, improve conventional efficient, have stability high using the method that the extraction system carries out water oxygen isotope analysis, favorable reproducibility, measuring accuracy is higher, it is accurate to analyze data, the advantages that effectively avoiding test data error caused by memory effect big.
Description
Technical Field
The invention relates to the technical field of stable isotope analysis, in particular to an extraction system of oxygen isotopes in water and a method for analyzing the oxygen isotopes in the water by using the extraction system.
Background
The composition and content of hydrogen and oxygen isotopes of natural water in nature are influenced by complex geophysical, geochemical and biochemical actions, and isotope fractionation is generated in the processes of evaporation and condensation. As a result of isotope fractionation, various natural waters have different isotope characteristics, which makes stable isotope technology widely applied in the fields of geology, hydrology and geology, atmospheric science, ecology and the like, and the stable isotope analysis of water is gradually one of modern research methods in the field of water science. The stable isotope composition of water is considered as the "fingerprint" of water and plays an increasingly important role in the research of analyzing dynamic processes such as water source, migration and mixing. In particular D and18o, which is considered stable in the absence of high temperature water-rock action and strong evaporation conditions, is the most ideal environmental isotope for tracing hydrodynamic processes.
As the application of the hydrogen-oxygen isotope technology is more and more extensive, the detection method is more and more. The methods currently used for detecting hydrogen and oxygen isotopes mainly include: off-line double-path sample injection isotope ratio mass spectrometry (Dual-inlet IRMS), continuous flow water balance method Gasbench-IRMS and thermal conversion element analysis isotope ratio mass spectrometry (TC/EA-IRMS). The Dual-inlet IRMS is also the method for measuring the hydrogen-oxygen isotope composition in a sample by applying the earliest isotope ratio, has the characteristics of high analysis precision and accuracy, and is the most classical method in the hydrogen-oxygen isotope analysis method.
For the analysis of oxygen isotopes in water, the most widespread method at present is the carbon dioxide-water equilibrium exchange reaction, and the oxygen isotope exchange reaction between carbon dioxide isotopes and water is shown as the following formula:
C16O16o (gas) + H2 18O (liquid) ═ C16O18O (gas) + H2 16O (liquid)
The degree of fractionation of the oxygen isotope between carbon dioxide and water, typically by the oxygen isotope fractionation coefficient (α)CO2-H2O) Expressed as the quotient of the ratio of the carbon dioxide to the oxygen isotopes in water, the calculated expression is as follows:
under the condition of exchanging the carbon dioxide and the oxygen isotopes in the water, the carbon dioxide and the water reach the oxygen isotopes for exchanging, and after the exchange reaches the balance, the quotient of the ratio of the oxygen isotopes in the carbon dioxide and the water reaches the fractional distillation coefficient.
Generally, the carbon dioxide-water balance exchange reaction process mainly comprises the following three steps:
(1) the gaseous carbon dioxide dissolves into the water, i.e.:
CO2(gas) - - - -CO2(liquid)
(2) In a solution with a pH <8, carbon dioxide hydrates with water, i.e.:
H2O+CO2(liquid) - - -H2CO3
(3) The carbon dioxide undergoes dehydration and diffuses from the water into the gas phase, namely:
CO2(liquid) - - - -CO2(gas)
In the existing method for detecting hydrogen and oxygen isotopes, the Gasbench-IRMS adopts an on-line detection method, has the advantages of quick operation, high efficiency and the like, but has the defects of large sample consumption, high requirement on temperature stability, obvious memory effect and the like. The TC/EA-IRMS is established and continuously perfected based on a testing technology of a carbon reduction high-temperature conversion principle, realizes online simultaneous testing of hydrogen and oxygen isotopes in trace water step by step, and has the characteristics of convenience, rapidness and high precision, but the memory effect is obvious. For conventional samples (such as underground water), the ideal data can be obtained by the methods, but for samples added with the tracer, the online continuous flow method usually has obvious memory effect and large error of measured data. For the off-line two-way sampling method for testing the oxygen isotope of the liquid sample, Yufuji et al disclose the method for measuring the oxygen isotope of ultra-micro water (Yufuji, Liudebin, Lu-shou)2-H2O Normal temperature equilibrium method ([ J ]]Scientific report, 1990,35(9): 690-. In addition, in the Gasbench-IRMS detection method, the balancer for providing carbon dioxide-water equilibrium exchange reaction is usually processed at constant temperature in a fixed heatable sample plate, which is not favorable for sufficient mixing exchange of carbon dioxide and water; in the above off-line detection method, the balancer for providing carbon dioxide-water equilibrium exchange reaction is usually removed from the operation platform after the vacuumization process is completed, and then moved to an additional device for equilibrium exchange reaction, and after the carbon dioxide and the oxygen isotope in water reach the exchange equilibrium,and the balancer is connected to the sample collection unit again for sampling carbon dioxide, so that the operation is complex and the carbon dioxide-water balance exchange process cannot be kept constant. Therefore, in the current method for detecting hydrogen and oxygen isotopes, no matter an online detection method or an offline detection method, the balance unit and the sample collection unit cannot be well integrated, and the accuracy of sample testing is affected.
Therefore, the development of a method for analyzing the oxygen isotope in water and a device for implementing the method, which are convenient, fast, efficient, high in precision, capable of improving the memory effect, capable of well integrating the balance unit and the sample collection unit into a whole, capable of guaranteeing the consistency of sample preparation, capable of reducing the loss of the sample to the maximum extent, high in stability and good in reproducibility, becomes a problem to be solved urgently in the field of the current oxygen isotope in water analysis.
Disclosure of Invention
The invention aims to overcome the defects of high requirement on temperature stability, poor repeatability of measured data, low precision, larger error of analysis data, incapability of fully mixing and exchanging carbon dioxide and water and the like in an online detection method, which are caused by obvious memory effect, and the defects of low efficiency of a sample preparation process, complex operation means, easy sample loss, influence on test precision and the like in an offline detection method in the existing water oxygen isotope analysis method, and provides an extraction system of an oxygen isotope in water and a method for analyzing the oxygen isotope in water by using the extraction system. According to the principle of a water balance method, the invention designs a pretreatment platform, and the balance unit and the sample collection unit are well integrated into a whole, namely the extraction system of the oxygen isotope in water simplifies the experiment operation and improves the experiment efficiency. The extraction system provided by the invention can be used for oxygen isotope analysis of a conventional water sample, and can also be used for oxygen isotope analysis of liquid samples such as a water sample containing a tracer and a urine sample.
In order to achieve the above object, a first aspect of the present invention provides an extraction system for oxygen isotopes in water, the extraction system including a balancing unit, a sample collection unit, and a vacuum unit, wherein the vacuum unit includes a vacuum main line pipeline, and a first mechanical pump and a second mechanical pump respectively communicated with two ends of the vacuum main line pipeline, the balancing unit and the sample collection unit are communicated with each other through a connecting pipeline and are sequentially connected to the vacuum unit along the vacuum main line pipeline, and a carbon dioxide supply device and a molecular pump are disposed between the balancing unit and the first mechanical pump; wherein,
the balance unit comprises a plurality of balancers, a control panel module and a heat treatment device for keeping the balancers at a constant temperature, wherein independent gas circuit pipelines which are correspondingly communicated with the balancers one by one, electromagnetic valves for controlling the opening and closing of the independent gas circuit pipelines and a controller for controlling the balancers to synchronously reciprocate in the heat treatment device along the horizontal direction are arranged in the control panel module;
the sample collection unit comprises a main sample collection pipeline, and a primary cold trap, a secondary cold trap and a plurality of sample collection pipes which are sequentially connected and arranged along the main sample collection pipeline.
In a second aspect, the present invention provides a method for performing an isotope analysis of oxygen in water using the aforementioned extraction system, the method comprising:
(i) placing a plurality of balancers for collecting water samples on a fixed carrier, connecting the balancers to the vacuumizing main pipeline through respective independent gas circuit pipelines, and opening the electromagnetic valves in the control panel module to enable the gas circuit pipelines of the balancers to be communicated with the vacuumizing main pipeline;
(ii) vacuumizing all balancers and pipelines in the balancing unit to a preset vacuum degree, introducing carbon dioxide into the balancers, stopping introducing standard carbon dioxide after the pressure of each balancer reaches a preset pressure, closing electromagnetic valves in a control panel module, enabling the gas pipeline of each balancer and the vacuumizing main pipeline to be in a disconnected state, keeping for 2-5 minutes, controlling the fixed carrier frame and the balancers to synchronously reciprocate in the horizontal direction in the heat treatment device, and performing carbon dioxide-water balance exchange of carbon dioxide and oxygen elements in water;
(iii) after the carbon dioxide-water balance exchange in the step (ii) is finished, the primary cold trap, the secondary cold trap and each sample collecting pipe in the sample collecting unit are vacuumized to a preset vacuum degree, and the primary cold trap, the secondary cold trap and the sample collecting pipe are respectively frozen by using refrigerating devices filled with cold liquids with different temperatures, then the electromagnetic valve in the control panel module is opened to control the independent gas pipeline at the top of the balancer to sequentially release carbon dioxide obtained after carbon dioxide-water balance exchange, the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange sequentially passes through the primary cold trap and the secondary cold trap to remove moisture and organic hydrocarbon gas, purifying the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange, and then sequentially freezing and collecting the purified carbon dioxide through each sample collecting pipe;
(iv) and completely collecting carbon dioxide obtained after carbon dioxide-water balance exchange, taking down the sample collecting pipes one by one, connecting the sample collecting pipes to a sample inlet of an oxygen isotope analysis instrument, releasing the carbon dioxide in the sample collecting pipes, and carrying out oxygen isotope analysis to obtain the oxygen isotope ratio in the carbon dioxide.
Through the technical scheme, the method can be used for rapidly and efficiently analyzing the oxygen isotope in the water, is high in precision, accurate in analysis result and good in repeatability in the analysis process, can effectively avoid test data errors caused by memory effect, is simple and convenient to operate, integrates the balance unit and the sample collection unit into a whole well, can prepare a plurality of samples simultaneously, guarantees the continuity of sample preparation, reduces the loss of the samples to the maximum extent, and is stronger in operability and higher in analysis efficiency compared with the traditional offline analysis and detection method.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural diagram of a system for extracting oxygen isotopes from water according to the present invention;
FIG. 2 is a schematic top view of the balancer disposed on the fixed carrier in a concentric circle array in the system for extracting oxygen isotopes from water according to the present invention;
FIG. 3 is a schematic top view of balancers arranged in a rectangular array on the fixed carrier in the system for extracting oxygen isotopes from water according to the present invention;
fig. 4 is a schematic structural diagram of a sample collection tube in the system for extracting an oxygen isotope in water according to the present invention.
Description of the reference numerals
1. Balance unit 11, fixed carrier 12, balancer 13, and heat treatment apparatus
14. Control panel module 15, screwed joint 16, vacuum pumping auxiliary pipeline 2 and sample collection unit
21. Primary cold trap 22, secondary cold trap 23, sample collecting pipe 24 and grease sealing joint
3. Vacuumizing unit 31, first mechanical pump 32, second mechanical pump 33 and vacuumizing main pipeline
41. A connecting pipeline 42, a main sample collecting pipeline 51, a first vacuum gauge 52 and a second vacuum gauge
6. Carbon dioxide supply device 7, molecular pump V1, first valve V2, second valve
V3, a third valve V4, a fourth valve V5, a fifth valve V6 and a sixth valve
V7, seventh valve V8, eighth valve V9, ninth valve
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the terms of orientation such as "upper, lower, top, bottom" used herein generally refer to the orientation with respect to the schematic structural view of the system for extracting an oxygen isotope from water in the present invention, for example, the term of orientation such as "lower" of a container or a member as referred to herein refers to the position from the bottom to 1 to 40% of the height of the container or member, and the term of "top" of the container or member refers to the position from the bottom to 90 to 100% of the height of the container or member. "inside and outside" are defined with respect to the actual structure of the extraction system of the oxygen isotopes in water.
As described above, the present invention provides an extraction system of oxygen isotopes in water, comprising a balancing unit 1, a sample collection unit 2, and an evacuation unit 3; the vacuumizing unit 3 comprises a vacuumizing main pipeline 33, and a first mechanical pump 31 and a second mechanical pump 32 which are respectively communicated with two ends of the vacuumizing main pipeline 33; the balance unit 1 and the sample collection unit 2 are communicated through a connecting pipeline 41 and are connected to the vacuumizing unit 3; a carbon dioxide supply device 6 and a molecular pump 7 are arranged between the balancing unit 1 and the first mechanical pump 31; wherein,
the balancing unit 1 includes a plurality of balancers 12, a control panel module 14, and a heat treatment device 13 for keeping the balancers 12 at a constant temperature; independent gas circuit pipelines which are communicated with the balancers 12 in a one-to-one correspondence mode, electromagnetic valves for controlling the opening and closing of the independent gas circuit pipelines and a controller for controlling the balancers 12 to synchronously reciprocate in the horizontal direction in the heat treatment device 13 are arranged in the control panel module 14;
the sample collection unit 2 comprises a main sample collection pipeline 42, and a primary cold trap 21, a secondary cold trap 22 and a plurality of sample collection pipes 23 which are arranged on the main sample collection pipeline 42 and communicated in sequence.
According to the extraction system provided by the invention, the carbon dioxide supply device 6 is used for supplying standard carbon dioxide gas, for example, the carbon dioxide supply device 6 can be a steel carbon dioxide gas cylinder. Among the standard carbon dioxide gas, CO2Has a purity of 99.99% or more, and the carbon dioxide in the carbon dioxide replenishing device 6 has an oxygen isotope ratio R to carbon dioxide before useCO2Pre-calibration is carried out, R isCO2Is equal to CO2In18O and16weight ratio of O
According to the extraction system provided by the invention, the control panel 14 in the balancing unit 1 is internally provided with the independent gas circuit pipelines which are correspondingly communicated with each balancer 12 one by one, so that residual samples attached in the main pipeline or the auxiliary pipeline can be effectively reduced, mutual pollution of the samples among the balancers is avoided, and the interference of the memory effect on sample testing is eliminated. The electromagnetic valve arranged in the control panel 14 can intelligently control the opening and closing of each independent air pipeline, and flexibly adjust the connection or disconnection state between the balancer 12 and the vacuumizing main pipeline 33. The controller arranged in the control panel 14 can control the balancers 12 to synchronously reciprocate in the heat treatment device 13 along the horizontal direction, so that water and carbon dioxide in each balancer 12 can be fully mixed, carbon dioxide-water balance exchange reaction can be fully performed, and the carbon dioxide-water balance exchange reaction performed in each balancer 12 can be guaranteed to be performed under the same condition, so that the balance unit 1 and the sample collection unit 2 can be well integrated into the same sample pretreatment platform.
According to the extraction system of the present invention, the control panel 14 controls the balancer 12 to reciprocate synchronously in the horizontal direction in the thermal processing device 13, for example, by arranging an oscillating table in the balancing unit 1, and the controller in the control panel 14 controls the state of starting or stopping the oscillating table, and adjusts the oscillating speed and the oscillating amplitude of the oscillating table.
According to the extraction system provided by the present invention, the balancing unit 1 further comprises a fixed carrier 11, and in order to keep each balancer 12 in the same state to the maximum, the balancers 12 are preferably uniformly distributed on the fixed carrier 11, for example, the uniformly distributed manner may comprise: concentric circular arrays and/or regular polygonal arrays.
According to the present invention, as shown in fig. 2, the concentric circular array may be distributed in the following manner: the centers of the balancers 12 may be distributed on a plurality of circumferential lines concentric with the center of the fixed carrier 11, the distance between two adjacent circumferential lines is equal, and the distance between the centers of two adjacent balancers 12 distributed on the same circumferential line is equal.
According to the present invention, the regular polygonal array may be distributed in a parallelogram array, an isosceles trapezoid array, a regular polygonal array, or the like, as long as the distance between the centers of two adjacent balancers 12 located in the same row and the distance between the centers of two adjacent balancers 12 located in the same column are respectively equal. For example, as shown in fig. 3, the balancers 12 may be arranged in a rectangular array distribution of 3 rows by 8 columns.
According to the present invention, the shape and size of the balancer 12 are not particularly limited as long as a sufficient water sample can be accommodated for the carbon dioxide-water equilibrium exchange reaction with carbon dioxide and a sufficient amount of carbon dioxide gas for the detection analysis by an isotope analyzer such as a mass spectrometer can be generated after the carbon dioxide-water equilibrium exchange reaction. For example, the balancer 12 may be a concentric reducer pipe with a top portion being a reduced diameter injection port and a bottom portion being a reduced diameter tubular container, the inner diameter of the reduced diameter injection port of the balancer 12 may be 0.5-0.8cm, and the height may be 1-1.5 cm; the height of the radial tubular container of the balancer 12 may be 3-5cm, and the inner diameter may be 1.5-2.5 cm.
According to the present invention, the material of the balancer 12 is not particularly limited as long as it has good sealing property and moderate thermal conductivity, and it may be, for example, a glass container, a quartz container, or the like.
According to the extraction system provided by the invention, the primary cold trap 21 and the secondary cold trap 22 are used for purifying the carbon dioxide gas from the balance unit 1, and the sample collection pipe 23 is used for collecting the purified carbon dioxide gas.
According to the present invention, the shape and size of the sample collection tube 23 are not particularly limited as long as it can collect only enough carbon dioxide released after carbon dioxide-water equilibrium exchange from the equilibration unit 1 and meet the sample standard for loading with an oxygen isotope analyzer, such as an isotope mass spectrometer. For example, the sample collection tube 23 may be a tubular container, and the height of the sample collection tube 23 may be 5 to 10cm, and the inner diameter may be 0.5 to 1.5 cm.
According to the present invention, the material of the sample collection tube 23 is not particularly limited as long as it has good sealing properties and moderate thermal conductivity, and may be, for example, a glass container, a quartz container, or the like.
According to the extraction system provided by the invention, the balancer 12 and the sample collection pipe 23 are arranged in a detachable mode.
Preferably, the balancing unit 1 may further include at least one vacuum-pumping sub-pipeline 16, the vacuum-pumping sub-pipeline 16 is communicated with the vacuum-pumping main pipeline 33 through a vacuum-pumping branch pipeline, the sample inlet of the balancer 12 is a threaded sample inlet, the vacuum-pumping sub-pipeline 16 is provided with a plurality of independent gas circuits having threaded connectors 15 matched with the threaded sample inlet of the balancer 12 in size, and the independent gas circuits are used for connecting the respective balancers 12 into the vacuum-pumping sub-pipeline 16. The independent gas circuit can be a stainless steel pipe welded on the vacuumizing auxiliary pipeline 16, and the bottom of the stainless steel pipe is provided with a threaded joint 15. In order to ensure the airtightness of the balancing unit 1, it is preferable that the threaded joint 15 is a high-vacuum threaded joint.
Preferably, in order to facilitate the collection of the carbon dioxide sample and control the connection or disconnection of the pipelines in the sample collection pipe 23 and the sample collection unit 2 and the sample introduction pipeline finally connected to the sample analyzer, as shown in fig. 4, the sidewall of the sample collection pipe 23 is provided with a sample collection pipe orifice, the top of the sample collection pipe 23 is provided with a sealing piston, the sample collection pipe orifice and the sealing piston are grease sealing ports, and the sample collection main pipeline 42 is provided with a plurality of grease sealing joints 24 matched with the grease sealing ports of the sample collection pipe 23 in size for connecting each sample collection pipe 23 to the sample collection main pipeline 42. In the present invention, the grease tight joint 24 may be a glass ground joint, and in order to ensure the air tightness of the sample collection unit 2, it is preferable that an outer surface of the grease tight port of each sample collection tube 23 and an inner surface of each grease tight joint 24 are coated with vacuum grease before the grease tight port of each sample collection tube 23 is connected to the grease tight joint 24.
According to the extraction system provided by the invention, the sample collection unit 2 further comprises a refrigerating device filled with acetone and liquid nitrogen mixed cold liquid for freezing the primary cold trap 21, a refrigerating device filled with ethanol and liquid nitrogen mixed cold liquid for freezing the secondary cold trap 22 and a refrigerating device filled with liquid nitrogen for freezing the sample collection pipe 23.
According to the invention, under the standard atmospheric pressure, the boiling point of carbon dioxide is-78.4 ℃, when the balance unit 1 releases carbon dioxide, the wall temperature of the primary cold trap 21 reaches-70 to-80 ℃ by the refrigerating device filled with the acetone and liquid nitrogen mixed cold liquid, and water vapor and organic hydrocarbon gas with the boiling point higher than that of the carbon dioxide in the carbon dioxide from the balance unit 1 can be removed by freezing; the refrigerating device filled with the mixed cold liquid of ethanol and liquid nitrogen enables the wall temperature of the secondary cold trap 22 to reach-80 to-90 ℃, water vapor in the carbon dioxide of the self-balancing unit 1 and organic hydrocarbon gas with boiling point higher than that of the carbon dioxide can be further frozen and removed, and the carbon dioxide is purified; the refrigeration device filled with liquid nitrogen enables the wall temperature of the sample collection pipe 23 to reach-194 to-198 ℃, and can effectively freeze and collect the purified carbon dioxide from the balance unit 1.
Preferably, in order to extend the flowing distance of the water vapor and the organic hydrocarbon gas entrained in the gaseous carbon dioxide released after the carbon dioxide-water equilibrium exchange in the balancing unit 1 as much as possible and ensure that the water vapor and the organic hydrocarbon gas are sufficiently removed, the primary cold trap 21 is a U-shaped tube cold trap, the secondary cold trap 22 is a tubular cold trap, and the size of the secondary cold trap 22 is set to be larger than that of the sample collecting tube 23.
Preferably, in order to ensure that the temperature difference between the inside of the balancer 12 and the material flow conveying pipelines in the balancing unit 1 and between the primary cold trap 21 and the secondary cold trap 22 and the material flow conveying pipelines in the sample collection unit 2 is sufficient under the action of the refrigerating device filled with cold liquid, and to prevent the residual impurity gas from attaching to the pipelines after the freezing collection of the carbon dioxide sample gas is completed, a memory effect is generated, so that the impurity water vapor and the organic hydrocarbon gas are respectively and maximally frozen and trapped by the primary cold trap 21 and the secondary cold trap 22, and further to effectively avoid the pollution of the pipeline inner walls by the residual impurity gas and the influence on the accuracy of the subsequent water oxygen isotope analysis test, the sample extraction system further comprises a heating element for adding the connecting pipelines in the balancing unit 1 and the sample collection unit 2, particularly the connecting pipeline 41 between the balancing unit 1 and the sample collection unit 2 and the sample collection main pipeline 42 (adding is performed) And (4) heating. The heating element may be a heating strip or a heating tape, and is wound around the outer wall of each line in the equilibration unit 1 and the sample collection unit 2 in a wound manner, preferably, the heating element provides a heating temperature of 40-60 ℃.
According to the extraction system provided by the present invention, the heat treatment device 13 is used for providing the temperature required to be maintained in the carbon dioxide-water balance exchange in the balancer 12, and the type of the heat treatment device 13 is not particularly limited as long as the aforementioned function can be achieved, and may be, for example, one of a water bath, a salt bath furnace, a sand bath furnace, a radiation furnace and a hollow electric heating furnace, preferably a water bath.
The extraction system provided by the invention also comprises a plurality of valves for controlling the communication state between each unit and the pipeline, and the setting conditions of the valves comprise:
a first valve V1 is arranged on a connecting pipeline between the carbon dioxide supply device 6 and the balancing unit 1 and is used for controlling the opening and closing of a standard carbon dioxide sample injection pipeline and/or adjusting the release flow of standard carbon dioxide;
a second valve V2 is arranged on the connecting line between the first mechanical pump 31 and the balancing unit 1, and is used for cooperatively controlling the starting and stopping of the vacuum-pumping unit 3 and the intensity of vacuum pumping in cooperation with the second mechanical pump 32;
a third valve V3 is arranged on a connecting line between the molecular pump 7 and the balancing unit 1 and is used for further controlling the vacuum intensity of the vacuum unit 3;
a fourth valve V4 is disposed on the connection line between the control panel module 14 and the fixed carrier 11 for controlling the connection and disconnection between the balancing unit 1 and the vacuum pumping unit 3;
a fifth valve V5 is arranged on the connecting pipeline 41 between the balancing unit 1 and the sample collecting unit 2 and is used for controlling the opening and closing of the connecting pipeline 41 between the balancing unit 1 and the sample collecting unit 2 and regulating the flow rate of the material flow in the connecting pipeline 41;
a sixth valve V6 is arranged on the connecting line between primary cold trap 21 and secondary cold trap 22, and is used for controlling the opening and closing of the connecting line between primary cold trap 21 and secondary cold trap 22 and regulating the flow rate of the material flow in the connecting line;
a seventh valve V7 is disposed on the connection line between the main sample collection line 42 and the vacuum main line 33, and is used for controlling the connection or disconnection between the sample collection unit 2 and the vacuum unit 3;
an eighth valve V8 is disposed at an end of the main sample collection pipeline 42 and is used for controlling the opening and closing of an end gas path of the sample collection unit 2;
a ninth valve V9 is disposed on the connecting line between the second mechanical pump 32 and the sample collection unit 2, and is used to cooperate with the first mechanical pump 31 to control the start and stop of the vacuum unit 3 and the intensity of vacuum.
According to the present invention, in order to secure the degree of vacuum of the extraction system, a first vacuum gauge 51 is provided on a connection line between the balancer 12 and the evacuation main line 33 to monitor the degree of vacuum of the balancing unit 1; a second vacuum gauge 52 is disposed on a connection line between the sample collection tube 23 and the evacuation main line 33 for monitoring the vacuum degree of the sample collection unit 2.
As described above, the second aspect of the present invention provides a method for performing an oxygen isotope analysis in water using the aforementioned extraction system for an oxygen isotope in water, the method comprising:
(i) placing a plurality of balancers 12 for collecting water samples on a fixed carrier 11, connecting the balancers to the vacuumizing main line 33 through respective independent gas line, and opening the solenoid valves in the control panel module 14 to enable the gas line of each balancer 12 to be in a communicated state with the vacuumizing main line;
(ii) vacuumizing each balancer 12 and pipeline in the balancing unit 1 to a preset vacuum degree, introducing standard carbon dioxide into the balancer 12, stopping introducing the standard carbon dioxide after the pressure of each balancer 12 reaches a preset pressure, closing an electromagnetic valve in a control panel module, keeping the gas pipeline of each balancer and the vacuumizing main pipeline in a disconnected state for 2-5 minutes, controlling the fixed carrier 11 and the balancer 12 to synchronously reciprocate in the heat treatment device 13 along the horizontal direction, and performing carbon dioxide-water balance exchange between the carbon dioxide and oxygen in water;
(iii) after the carbon dioxide-water balance exchange in the step (ii) is finished, the primary cold trap 21, the secondary cold trap 22 and each sample collection pipe 23 in the sample collection unit 2 are vacuumized to a predetermined vacuum degree, and the primary cold trap 21, the secondary cold trap 22 and the sample collecting pipe 23 are respectively frozen by using refrigerating devices filled with cold liquids with different temperatures, then the independent gas circuit pipeline at the top of the balancer 12 is controlled to sequentially release carbon dioxide obtained after carbon dioxide-water balance exchange, the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange sequentially passes through the primary cold trap 21 and the secondary cold trap 22 to remove moisture and organic hydrocarbon gas, purifying the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange, and then sequentially freezing and collecting the purified carbon dioxide through each sample collecting pipe 23;
(iv) and completely collecting carbon dioxide obtained after carbon dioxide-water balance exchange, taking down the sample collecting pipes 23 one by one, connecting the sample collecting pipes to a sample inlet of an oxygen isotope analysis instrument, releasing the carbon dioxide in the sample collecting pipes 23, and carrying out oxygen isotope analysis to obtain the oxygen isotope ratio in the carbon dioxide.
According to a specific embodiment of the present invention, the method for analyzing oxygen isotopes in water by using the above-mentioned system for extracting oxygen isotopes in water comprises the following steps:
(i) placing a plurality of balancers 12 for collecting water samples on the fixed carrier 11, connecting the balancers to the vacuum-pumping main pipeline 33 through respective independent gas pipelines, and opening the solenoid valves in the control panel module 14 to enable the gas pipelines of the balancers 12 to be in a communicated state with the vacuum-pumping main pipeline;
(ii) opening switches of a second valve V2, a third valve V3, a fourth valve V4 and a ninth valve V9, and a first mechanical pump 31, a second mechanical pump 32 and a molecular pump 7, vacuumizing each balancer 12 and pipeline in the balancing unit 1 to a predetermined vacuum degree, closing the second valve V2, the third valve V3, the fourth valve V4 and the ninth valve V9, opening switches of the first valve V1 and the carbon dioxide supply device 6, introducing standard carbon dioxide into the balancer 12, closing the switches of the fourth valve V4 and the carbon dioxide supply device 6 and a solenoid valve in a control panel module after the pressure of each balancer 12 reaches a predetermined pressure, keeping the gas pipeline of each balancer disconnected from the vacuumizing main pipeline for 2-5 minutes, and then opening a controller switch in the control panel module 14, controlling the fixed carrier 11 and the balancer 12 to synchronously reciprocate in the heat treatment device 13 along the horizontal direction, and performing carbon dioxide-water balance exchange of carbon dioxide and oxygen in water;
(iii) after the carbon dioxide-water balance exchange in step (ii) is finished, opening the second valve V2, the third valve V3, the seventh valve V7 and the ninth valve V9, vacuumizing the primary cold trap 21, the secondary cold trap 22 and each sample collecting pipe 23 in the sample collecting unit 2, closing the second valve V2, the third valve V3, the seventh valve V7 and the ninth valve V9 when the second vacuum gauge 52 displays that the vacuum degree reaches a predetermined vacuum degree, freezing the primary cold trap 21, the secondary cold trap 22 and the sample collecting pipe 23 by using refrigeration devices filled with cold liquids with different temperatures, opening the fifth valve V5 and the sixth valve V6, then opening the electromagnetic valve in the control panel module 14, controlling the independent gas pipeline at the top of the balancer 12 to release balanced carbon dioxide obtained after the carbon dioxide-water balance exchange, wherein the carbon dioxide obtained after the carbon dioxide-water balance exchange sequentially passes through the primary cold trap 21, the third valve V3, the seventh valve V3938 and the ninth valve V9, The secondary cold trap 22 removes moisture and organic hydrocarbon gas, purifies the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange, then the purified carbon dioxide is frozen and collected by each sample collection pipe 23, and when the carbon dioxide in each balancer 12 is completely released, the sixth valve V6, the seventh valve V7 and the eighth valve V8 are closed;
(iv) and completely collecting carbon dioxide obtained after carbon dioxide-water balance exchange, rotating a sealing piston at the top of the sample collecting pipe 23 to keep the sample collecting pipe 23 disconnected from the main sample collecting pipeline 42, taking down the sample collecting pipes 23 one by one, then connecting a sample collecting pipe opening on the side wall of the sample collecting pipe 23 into a sample inlet of an oxygen isotope analysis instrument, rotating the sealing piston at the top of the sample collecting pipe 23 to keep the sample collecting pipe 23 communicated with the sample inlet of the oxygen isotope analysis instrument, releasing the carbon dioxide in the sample collecting pipe 23, and performing oxygen isotope analysis to obtain the oxygen isotope ratio in the carbon dioxide.
The method for the isotopic analysis of oxygen in water provided by the invention is characterized in that air (containing CO) remained in each container and pipeline in the balancing unit 1 is eliminated as much as possible2Gas) to prevent interference with the sample, carbon dioxide is being carried outBefore the water balance exchange reaction, in step (ii), it is preferable to evacuate each balancer 12 and the line in the balancing unit 1 until the first vacuum gauge 51 shows a degree of vacuum of 0.1 torr or more.
According to the method for the isotopic analysis of oxygen in water provided by the invention, Torr is the transliteration of pressure unit Torr, and 1 Torr is equivalent to the pressure of 1 mm mercury column at 25 deg.C (298.15K), i.e. about 133.3224 Pa.
In the method for analyzing oxygen isotope in water according to the present invention, in order to provide sufficient standard carbon dioxide to perform carbon dioxide-water equilibrium exchange reaction with the water sample, in step (ii), the standard carbon dioxide is preferably introduced into the balancer 12 in an amount such that the pressure of the balancer 12 reaches 450-.
According to the method for the isotope analysis of oxygen in water provided by the invention, in the step (ii), the conditions for the water balance exchange of carbon dioxide and oxygen element in water comprise: the temperature of the heat treatment device 13 is controlled to be 20-30 ℃, and the water balance exchange time is 2.5-4 hours.
The method for the isotopic analysis of oxygen in water according to the present invention is provided, wherein, in order to exclude as much as possible the air (including CO) remaining in each container and pipeline in the sample collection unit 22Gas) to prevent interference with the sample, and before the carbon dioxide sample collection is performed, in step (iii), the primary cold trap 21, the secondary cold trap 22, and each sample collection tube 23 in the sample collection unit 2 are evacuated until the second vacuum gauge 52 indicates a degree of vacuum of 0.1 torr or more.
According to the method for analyzing the oxygen isotope in water provided by the invention, in order to enable the wall temperature of the primary cold trap 21 to reach-70 to-80 ℃ when the primary cold trap is placed in a refrigerating device filled with cold liquid under the standard atmospheric pressure, so as to freeze and remove water vapor and organic hydrocarbon gas with a boiling point higher than that of the carbon dioxide in the carbon dioxide from the balance unit 1, and prolong the time for which the cold liquid can be stably stored as far as possible, the cold liquid in the refrigerating device for freezing the primary cold trap 21 is preferably acetone and liquid nitrogen mixed cold liquid, and the volume ratio of the acetone to the liquid nitrogen is further preferably 0.5-1: 1.
according to the method for the water oxygen isotope analysis provided by the invention, under the standard atmospheric pressure, in order to enable the secondary cold trap 22 to be placed in a refrigeration device filled with cold liquid, the wall temperature can reach-80 to-90 ℃ so as to further freeze and remove water vapor and organic hydrocarbon gas with a boiling point higher than that of the carbon dioxide in the carbon dioxide from the balance unit 1, the cold liquid in the refrigeration device for freezing the secondary cold trap 22 is preferably ethanol and liquid nitrogen mixed cold liquid, and the volume ratio of the ethanol to the liquid nitrogen is further preferably 1-1.5: 1.
according to the method for the water oxygen isotope analysis provided by the invention, in order to effectively freeze and collect purified carbon dioxide from the balancing unit 1 under the standard atmospheric pressure, the cold liquid in the refrigerating device for freezing the sample collecting pipe 23 is liquid nitrogen, so that when the sample collecting pipe 23 is placed in the refrigerating device filled with liquid nitrogen, the wall temperature of the sample collecting pipe 23 can reach-194 to-198 ℃, and the gaseous carbon dioxide in the pipeline can be fully frozen and collected.
According to the method for analyzing the oxygen isotope in water provided by the invention, in order to ensure that sufficient temperature difference exists between the inside of the balancer 12 and the material flow conveying pipelines in the balancing unit 1 and between the primary cold trap 21 and the secondary cold trap 22 and the material flow conveying pipelines in the sample collecting unit 2 under the action of a refrigerating device filled with cold liquid and prevent residual impurity gas from attaching to the pipelines after the freezing and collecting of the carbon dioxide sample gas are finished, a memory effect is generated, so that the impurity water vapor and the organic hydrocarbon gas are respectively and maximally frozen and collected by the primary cold trap 21 and the secondary cold trap 22, the pollution of the inner walls of the pipelines by the residual impurity gas is effectively avoided, the accuracy of the subsequent oxygen isotope analysis and test in water is influenced, in the step (iv), the carbon dioxide frost frozen and collected in the sample collecting pipe 23 does not grow any more, which indicates that the carbon dioxide obtained after the carbon dioxide-water balance exchange is completely collected, closing the sealing piston at the top of the sample collection tube 23, and after removing the sample collection tubes 23 one by one, opening the switch of the heating element (heating strip or heating tape) wound around the outer wall of each of the pipelines in the balancing unit 1 and the sample collection unit 2 in a winding manner in the extraction system, and heating each of the pipelines in the balancing unit 1 and the sample collection unit 2 to 40-60 ℃.
According to the method for analyzing the oxygen isotope in water provided by the invention, in the step (iv), before the sample collection pipe 23 is connected to the oxygen isotope analysis instrument, the method further comprises the step of vacuumizing a sample introduction pipeline of the oxygen isotope analysis instrument until the vacuum degree is stabilized at 10-3-10-4And Pa, rotating a sealing piston at the top of the sample collecting pipe 23 to enable the sample collecting pipe 23 and a sample introduction pipeline of the oxygen isotope analysis instrument to be in a communicated state, releasing carbon dioxide, completing sample introduction, and performing oxygen isotope analysis to obtain the oxygen isotope ratio in the carbon dioxide obtained after the detected water sample and the carbon dioxide are subjected to oxygen isotope exchange balance.
According to the present invention, the oxygen isotope analysis apparatus may be a mass spectrometer.
According to the invention, when a mass spectrometer is used for oxygen isotope composition analysis, a multi-receiver is adopted to simultaneously collect ions of carbon dioxide (mass numbers of 44, 45 and 46) of a sample to be detected and standard carbon dioxide (mass numbers of 44, 45 and 46) which are obtained by carrying out oxygen isotope exchange balance on a water sample to be detected and carbon dioxide, and through two-way sample introduction, the carbon dioxide of the sample to be detected enters a sample bin during sample introduction, the standard carbon dioxide enters a standard bin, the analysis results of the carbon dioxide of the sample to be detected and the standard carbon dioxide are compared by a computer, and delta of the water sample to be detected relative to the oxygen isotope composition of the standard water sample is directly calculated18The O value (‰) is expressed by the ratio of the O value to the corresponding isotope in the standard water sample, and is calculated according to the following formula:
in the formula: SA represents the tested water sample, and ST represents the standard water sample.
According to the invention, due to the ingenious design of the balance unit 1 and the sample collection unit 2, the continuity of sample preparation is effectively ensured, and compared with the traditional analysis method in which the same vacuum treatment device is used for testing different samples, independent gas circuit pipelines are correspondingly arranged for each balancer one by one, so that the memory effect is effectively reduced, and the mutual pollution among different water samples to be tested is avoided, therefore, the error of oxygen isotope analysis in water is reduced to the maximum extent, the error is-0.2 thousandths, and the error is obtained by statistics according to the difference value between the result obtained by analyzing a large number of standard water samples and the standard value of the standard water sample.
The present invention will be described in detail below by way of examples.
In the following embodiments, the mass spectrometer is a mass spectrometer manufactured by Thermo Fisher corporation and having a model of Delta S, carbon dioxide of a sample to be detected, which is obtained by subjecting a water sample to be detected and carbon dioxide to oxygen isotope exchange equilibrium, is detected by a Dual-injection system (Dual-Inlet) of the mass spectrometer, and the sample is measured under a signal intensity of 4000-7000 mV.
In the following examples, the international Standard substance is Standard Mean Ocean Water (SMOW), and the delta of the measured water sample is18The O value (‰) represents the oxygen isotope composition of the water sample to be detected, and is expressed by the ratio of the oxygen isotope composition to the corresponding isotope in the standard average ocean water (V-SMOW), and is calculated according to the following formula:
in the formula, SA represents a sample, SMOW represents standard average ocean water.
Examples 1 to 24
(i) An extraction system as shown in figure 1 is adopted, twenty-four balancers 12 for collecting water samples are arranged on a fixed carrier 11 and are connected to a vacuumizing main pipeline 33 through independent gas pipelines, electromagnetic valves in a control panel module 14 are opened to enable the gas pipelines of the balancers 12 to be in a communicated state with the vacuumizing main pipeline, wherein as shown in figure 3, the balancers 12 are uniformly distributed on the fixed carrier 11 in a 3-row-by-8-column rectangular array mode, each balancer 12 is a concentric reducer pipe glass container with a reducing injection port of which the inner diameter is 0.5cm and the height is 1cm, a reducer pipe container of which the height is 5cm and the inner diameter is 2cm, a sample injection port of each balancer 12 is a threaded injection port, and a plurality of stainless steel pipes which are welded on a vacuumizing auxiliary pipeline 16 and are provided with threaded joints 15 matched with the threaded injection ports of the balancers 12 in size are independently sealed and connected with the gas pipelines in a detachable mode And (6) connecting.
(ii) Opening switches of a second valve V2, a third valve V3, a fourth valve V4 and a ninth valve V9, a first mechanical pump 31, a second mechanical pump 32 and a molecular pump 7, vacuumizing each balancer 12 and pipeline in the balancing unit 1 to be more than 0.1 Torr, closing the second valve V2, the third valve V3, the fourth valve V4 and the ninth valve V9, opening the first valve V1 and a switch of the carbon dioxide supply device 6, introducing standard carbon dioxide into the balancers 12, closing the switches of the fourth valve V4 and the carbon dioxide supply device 6 and a solenoid valve in a control panel module after the pressure of each balancer 12 reaches 500 Torr, keeping the gas pipeline of each balancer disconnected from the vacuumizing main pipeline for 3 minutes, opening a controller switch in the control panel module 14, controlling the fixed carrier rack 11 with the balancers 12 to be synchronously reciprocated in the horizontal direction in the heat treatment device 13 And (3) moving, performing carbon dioxide-water balance exchange of carbon dioxide and oxygen in water, controlling the temperature of the heat treatment device 13 to be 25 ℃, and controlling the carbon dioxide-water balance exchange time to be 4 hours, wherein the heat treatment device 13 is a water bath kettle.
(iii) After the carbon dioxide-water equilibrium exchange in step (ii) is completed, the second valve V2, the third valve V3, the seventh valve V7, and the ninth valve V9 are opened, the primary cold trap 21, the secondary cold trap 22, and each sample collection tube 23 in the sample collection unit 2 are evacuated, and when the second vacuum gauge 52 indicates a vacuum degree of 0.1 torr or more, the second valve V2, the third valve V3, the seventh valve V7, and the ninth valve V9 are closed, and the primary cold trap 21, the secondary cold trap 22, and the sample collection tube 23 are frozen using a refrigeration apparatus containing a mixed cold liquid of acetone and liquid nitrogen at-70 to-80 ℃, a refrigeration apparatus containing a mixed cold liquid of ethanol and liquid nitrogen at-80 to-90 ℃, and a refrigeration apparatus containing a cold liquid of liquid nitrogen at-194 to-198 ℃, respectively. And then, opening a fifth valve V5 and a sixth valve V6, then opening electromagnetic valves in the control panel module 14, controlling independent gas pipelines at the top of the balancers 12 to sequentially release carbon dioxide obtained after carbon dioxide-water equilibrium exchange, sequentially removing moisture and organic hydrocarbon gas from the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange through the primary cold trap 21 and the secondary cold trap 22, purifying the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange, sequentially freezing and collecting the purified carbon dioxide through each sample collection pipe 23, and closing the sixth valve V6, the seventh valve V7 and the eighth valve V8 after all the carbon dioxide in each balancer 12 is released. As shown in fig. 4, the sample collection pipe 23 is a tubular glass container with a side wall provided with a sample collection pipe orifice, a top provided with a sealing piston, a height of 8cm and an inner diameter of 1cm, the sample collection pipe orifice of each sample collection pipe 23 is a glass frosted orifice, and the glass frosted orifice connector 24 which is arranged on the sample collection main pipeline 42 and is matched with the glass frosted orifice of the sample collection pipe 23 in size is connected in a detachable manner by coating grease in a sealing manner.
(iv) And when the carbon dioxide frost frozen and trapped in the sample collecting pipe 23 does not grow any more, which indicates that the carbon dioxide obtained after the carbon dioxide-water equilibrium exchange is completely collected, rotating a sealing piston at the top of the sample collecting pipe 23 to keep the sample collecting pipe 23 disconnected from the main sample collecting pipeline 42, and taking down the sample collecting pipes 23 one by one. And then, a sample collecting pipe opening on the side wall of the sample collecting pipe 23 is connected to a sample inlet of a mass spectrometer, a sealing piston at the top of the sample collecting pipe 23 is rotated, so that the sample collecting pipe 23 is kept in a communicated state with the sample inlet of an oxygen isotope analysis instrument, carbon dioxide in the sample collecting pipe 23 is released, and oxygen isotope analysis is carried out to obtain the oxygen isotope ratio in the carbon dioxide.
Finally, the switch of the heating belt coiled on the outer wall of each pipeline in the balancing unit 1 and the sample collecting unit 2 in the extraction system is opened, and each pipeline in the balancing unit 1 and the sample collecting unit 2 is heated to 50 ℃ to remove the miscellaneous gas adsorbed on the pipe wall.
The kind, amount and test results of each water sample used in examples 1 to 24 are shown in table 1. In examples 1 to 24, the test samples subjected to isotope analysis in each example were carbon dioxide-water equilibrium exchange reactions of twenty-four different water samples simultaneously carried out in batches, and twenty-four carbon dioxide samples obtained by subjecting the water samples to be tested to oxygen isotope exchange equilibrium with carbon dioxide were collected one by one. The time for completing the carbon dioxide-water equilibrium exchange reaction of all the twenty-four water samples is only 4 hours, the time for collecting the carbon dioxide samples prepared from all the twenty-four water samples is 1.5 hours, and the total time for completing the extraction and preparation of the oxygen isotopes in the whole water of all the twenty-four water samples is about 6 hours.
TABLE 1
| Item numbering | Name of water sample | Water sample source | Water sample dosage in balancer (mL) | Measurement of delta18OSA-SMOW(‰) |
| Example 1 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -8.29 |
| Example 2 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -5.86 |
| Example 3 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -4.56 |
| Example 4 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -5.03 |
| Example 5 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -7.59 |
| Example 6 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -6.45 |
| Example 7 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -10.31 |
| Example 8 | SMOW | Standard sample | 5 | 0.10 |
| Example 9 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -2.34 |
| Example 10 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -1.11 |
| Example 11 | Urine (urinary incontinence) | Sending and measuring sample | 5 | 0.46 |
| Example 12 | Urine (urinary incontinence) | Sending and measuring sample | 5 | 1.40 |
| Example 13 | Urine (urinary incontinence) | Sending and measuring sample | 5 | 3.35 |
| Example 14 | Urine (urinary incontinence) | Sending and measuring sample | 5 | 7.64 |
| Example 15 | Urine (urinary incontinence) | Sending and measuring sample | 5 | 16.69 |
| Example 16 | SMOW | Standard sample | 5 | 0.16 |
| Example 17 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -1.80 |
| Example 18 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -8.26 |
| Example 19 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -5.94 |
| Example 20 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -7.53 |
| Example 21 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -2.42 |
| Example 22 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -5.26 |
| Example 23 | Urine (urinary incontinence) | Sending and measuring sample | 5 | -4.83 |
| Example 24 | SMOW | Standard sample | 5 | -0.06 |
Comparative examples 1 to 24
According to "oxygen isotope determination of ultra-trace water-capillary CO2-H2O Normal temperature equilibrium method ([ J ]]The same water samples as in examples 1-24 were tested by the oxygen isotope assay method for ultra-low water disclosed in scientific bulletin, 1990,35(9): 690-. In comparative examples 1 to 24, twenty-four water samples were collected by condensing twenty-four capillary tubes with liquid nitrogen, then carbon dioxide was introduced into the capillary tubes where the twenty-four water samples were collected by condensing, and then they were separately welded and sealed and taken off, and they were sent together into a thermostat of 25 ℃ to undergo carbon dioxide-water equilibrium exchange reaction for 24 hours, and then each welded and sealed capillary tube which completed carbon dioxide-water equilibrium exchange reaction was put into a cleaving device and placed in a vacuum system to cleave the tail of the capillary tube, releasing water and carbon dioxide after equilibrium, and they were condensed again in a cold trap, and then water and carbon dioxide were separated by a conventional distillation method, transferred to a sample tube, and connected to a mass spectrometer for measurement. The extraction preparation of the oxygen isotope in the whole water is completed by the twenty-four water samples, which takes about 36 hours.
The kind, amount and test results of each water sample used in comparative examples 1 to 24 are shown in Table 2.
TABLE 2
| Item numbering | Name of water sample | Water sample source | Water sample dosage in balancer (mu L) | Measurement of delta18OSA-SMOW(‰) |
| Comparative example 1 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -8.45 |
| Comparative example 2 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -5.78 |
| Comparative example 3 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -4.50 |
| Comparative example 4 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -5.23 |
| Comparative example 5 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -7.55 |
| Comparative example 6 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -6.38 |
| Comparative example 7 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -10.26 |
| Comparative example 8 | SMOW | Standard sample | 2 | 0.23 |
| Comparative example 9 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -2.34 |
| Comparative example 10 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -1.19 |
| Comparative example 11 | Urine (urinary incontinence) | Sending and measuring sample | 2 | 0.56 |
| Comparative example 12 | Urine (urinary incontinence) | Sending and measuring sample | 2 | 1.46 |
| Comparative example 13 | Urine (urinary incontinence) | Sending and measuring sample | 2 | 3.30 |
| Comparative example 14 | Urine (urinary incontinence) | Sending and measuring sample | 2 | 7.60 |
| Comparative example 15 | Urine (urinary incontinence) | Sending and measuring sample | 2 | 16.81 |
| Comparative example 16 | SMOW | Standard sample | 2 | 0.20 |
| Comparative example 17 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -1.88 |
| Comparative example 18 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -8.16 |
| Comparative example 19 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -5.99 |
| Comparative example 20 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -7.35 |
| Comparative example 21 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -2.37 |
| Comparative example 22 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -5.15 |
| Comparative example 23 | Urine (urinary incontinence) | Sending and measuring sample | 2 | -4.66 |
| Comparative example 24 | SMOW | Standard sample | 2 | -0.19 |
Examples 25 to 32
The extraction system used in examples 1 to 24 was used to analyze oxygen isotopes in water in the same manner as in examples 1 to 24, except that eight types of standard water samples were collected at random from the twenty-four balancers 12 uniformly distributed on the fixed carrier 11 in a rectangular array of 3 rows × 8 columns to perform carbon dioxide-water equilibrium exchange reaction in the eight types of balancers 12. After the carbon dioxide-water balance exchange reaction is finished, collecting three carbon dioxide samples obtained by performing oxygen isotope exchange balance on a standard water sample to be detected and carbon dioxide one by one for isotope analysis.
The kinds and amounts of each water sample used in examples 25 to 32, and the test results and the standard values of the oxygen isotope ratios in the water samples are shown in Table 3.
TABLE 3
Comparative examples 25 to 32
Eight kinds of standard water samples identical to those in examples 25 to 32 were tested by the continuous flow water equilibrium method GasBench-IRMS disclosed in "comparison of methods for analyzing Hydrogen and oxygen isotopes in Water by Flash HT and GasBench II-IRMS" (HongzhaoY, Liping Z, Meimei G, et al. method for analyzing Hydrogen and oxygen isotopes in Water [ J ]. report on Mass Spectrometry, 2013,34(6): 347-352.). In comparative examples 25 to 32, only 1 sample of carbon dioxide obtained by subjecting the water sample to be measured to oxygen isotope exchange equilibrium with carbon dioxide was prepared in each example, and the results of the tests in each example were each a test value of one collected sample of carbon dioxide obtained by subjecting the water sample to be measured to oxygen isotope exchange equilibrium with carbon dioxide.
The kinds and amounts of each water sample used in comparative examples 25 to 32, and the test results and the standard values of the oxygen isotope ratios in the water samples are shown in Table 4.
TABLE 4
Examples 33 to 35
The extraction system used in examples 1 to 24 was used to analyze oxygen isotopes in water according to the method of examples 1 to 24, except that three balancers 12 were selected among the twenty-four balancers 12 uniformly distributed on the fixed carrier 11 in a rectangular array of 3 rows × 8 columns to collect the same standard water sample for carbon dioxide-water equilibrium exchange reaction, wherein the three balancers 12 were selected in such a manner that one balancer 12 was randomly selected for each row in the rectangular array of 3 rows × 8 columns. After the carbon dioxide-water balance exchange reaction is finished, collecting three carbon dioxide samples obtained by carrying out oxygen isotope exchange balance on the water sample to be detected and carbon dioxide one by one for isotope analysis. The kinds and amounts of the standard water samples used in examples 33 to 35 and the test results and the standard values of the oxygen isotope ratios in the standard water samples are shown in Table 5.
Comparative examples 33 to 35
The analysis of oxygen isotopes in water was carried out according to the method of comparative examples 1-24, except that three identical standard water samples of examples 33-35 were collected by liquid nitrogen condensation using three capillary tubes. The kinds and amounts of the standard water samples used in comparative examples 33 to 35 and the test results and the standard values of the oxygen isotope ratios in the standard water samples are shown in Table 5.
Comparative examples 36 to 38
The analysis of oxygen isotopes in water was carried out in accordance with the method of comparative examples 25 to 32, except that the same standard water samples as those of examples 33 to 35 were subjected to parallel testing three times. The kinds and amounts of the standard water samples used in comparative examples 36 to 38 and the test results and the standard values of the oxygen isotope ratios in the standard water samples are shown in Table 5.
TABLE 5
Comparing the results of examples 1 to 24 and comparative examples 1 to 24, it can be seen that, when the method provided by the present invention is used for analyzing oxygen isotopes in water, the balance unit and the sample collection unit are well integrated, a plurality of samples can be simultaneously prepared, the continuity of sample preparation can be ensured, and the balancer can be synchronously driven to reciprocate, which is beneficial to the sufficient mixing of carbon dioxide and water under the same conditions, so that the exchange of carbon dioxide and oxygen isotopes in water is more thorough, and the method has the advantages of stronger operability, higher analysis efficiency and more accurate data analysis compared with the existing offline analysis detection method. In addition, the method provided by the invention simplifies the sample preparation process, greatly improves the preparation efficiency of the sample, saves the pretreatment time, and can meet the requirement of industrial analysis of a large number of samples.
Comparing the results of examples 25-32 and comparative examples 25-32, it can be seen that when the method provided by the present invention is used for analyzing oxygen isotopes in water, an independent gas circuit is provided for each balance unit, thereby effectively avoiding mutual contamination caused when the same pipeline is used for testing different water samples in the continuous flow water balance method Gasbench-IRMS analysis method, and finally obtaining high accuracy of the oxygen isotope ratio data in water. In the comparative examples 25-32, the balancer is subjected to constant temperature treatment by adopting the fixed heatable sample disc, so that the balancer is not beneficial to fully mixing and exchanging carbon dioxide and water, different balancers are subjected to vacuum pumping treatment by adopting a uniform pipeline, and when the oxygen isotope ratio in water is measured, the balancer has obvious memory effect, low data accuracy and poor repeatability.
Comparing the results of examples 33 to 35 with those of comparative examples 33 to 38, it can be seen that the synchronicity of each balancer in the extraction system provided by the present invention is high, and the reproducibility of the oxygen isotope ratio data in water finally obtained when the extraction system is used for the oxygen isotope analysis in water is good. In the comparative examples 33 to 38, the reproducibility of the test data was poor when the oxygen isotope analysis in water was performed on the same water sample by using the existing on-line analysis method or the existing off-line analysis method.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. An extraction system of oxygen isotopes in water, characterized in that it comprises a balancing unit (1), a sample collection unit (2) and an evacuation unit (3); the vacuumizing unit (3) comprises a vacuumizing main pipeline (33), and a first mechanical pump (31) and a second mechanical pump (32) which are respectively communicated with the two ends of the vacuumizing main pipeline (33); the balance unit (1) and the sample collection unit (2) are communicated through a connecting pipeline (41) and are connected to the vacuumizing unit (3); a standard carbon dioxide supply device (6) and a molecular pump (7) are arranged between the balancing unit (1) and the first mechanical pump (31); wherein,
the balancing unit (1) comprises a plurality of balancers (12), a control panel module (14) and a heat treatment device (13) for keeping the balancers (12) at a constant temperature; independent gas circuit pipelines which are correspondingly communicated with the balancers (12) one by one, electromagnetic valves for controlling the opening and closing of the independent gas circuit pipelines and a controller for controlling the balancers (12) to synchronously reciprocate in the horizontal direction in the heat treatment device (13) are arranged in the control panel module (14);
the sample collection unit (2) comprises a main sample collection pipeline (42), and a primary cold trap (21), a secondary cold trap (22) and a plurality of sample collection pipes (23) which are arranged on the main sample collection pipeline (42) and are communicated in sequence,
wherein the balancing unit (1) further comprises a fixed object carrier (11), the balancers (12) are uniformly distributed on the fixed object carrier (11) in a concentric circular array and/or a regular polygonal array,
wherein the balancer (12) and the sample collecting pipe (23) are arranged in a detachable mode,
the balance unit (1) further comprises at least one vacuumizing auxiliary pipeline (16), the vacuumizing auxiliary pipeline (16) is communicated with the vacuumizing main pipeline (33) through a vacuumizing branch pipeline, a sample inlet is formed in the top of the balancer (12) and is a threaded sample inlet, and a plurality of independent gas circuits with threaded connectors (15) matched with the threaded sample inlet of the balancer (12) in size are arranged on the vacuumizing auxiliary pipeline (16);
wherein the extraction system further comprises heating elements for heating the respective lines in the equilibration unit (1) and sample collection unit (2).
2. The extraction system according to claim 1, wherein the side wall of the sample collection tube (23) is provided with a sample collection nozzle, the top of the sample collection tube is provided with a sealing piston, the sample collection nozzle and the sealing piston are grease sealing ports, and the main sample collection pipeline (42) is provided with a plurality of grease sealing joints (24) matched with the grease sealing ports of the sample collection tube (23) in size.
3. Extraction system according to claim 1, wherein the sample collection unit (2) further comprises a refrigeration device with a mixed cold liquid of acetone and liquid nitrogen for freezing the primary cold trap (21), a refrigeration device with a mixed cold liquid of ethanol and liquid nitrogen for freezing the secondary cold trap (22) and a refrigeration device with liquid nitrogen for freezing the sample collection tube (23).
4. The extraction system according to claim 1, wherein the heat treatment device (13) is one of a water bath, a salt bath furnace, a sand bath furnace, a radiation furnace and a hollow electric heating furnace.
5. Extraction system according to claim 1, wherein the heat treatment device (13) is a water bath.
6. The extraction system according to claim 1, wherein a first valve (V1) is provided on the connecting line between the carbon dioxide make-up device (6) and the balancing unit (1);
a second valve (V2) is arranged on a connecting line between the first mechanical pump (31) and the balancing unit (1);
a third valve (V3) is arranged on a connecting pipeline between the molecular pump (7) and the balance unit (1);
a fourth valve (V4) is arranged on a connecting pipeline between the control panel module (14) and the fixed object carrier (11);
a fifth valve (V5) is arranged on a connecting pipeline (41) between the balance unit (1) and the sample collection unit (2);
a sixth valve (V6) is arranged on a connecting line between the primary cold trap (21) and the secondary cold trap (22);
a seventh valve (V7) is arranged on a connecting pipeline between the main sample collecting pipeline (42) and the vacuumizing main pipeline (33);
an eighth valve (V8) is arranged at the end part of the main sample collecting pipeline (42);
a ninth valve (V9) is provided in the connecting line between the second mechanical pump (32) and the sample collection unit (2).
7. Extraction system according to claim 1, wherein a first vacuum gauge (51) is provided on the connection line between the balancer (12) and the evacuation main line (33);
and a second vacuum gauge (52) is arranged on a connecting pipeline between the sample collecting pipe (23) and the vacuumizing main pipeline (33).
8. A method for performing an oxygen isotope analysis in water using the system for extracting an oxygen isotope in water as set forth in any one of claims 1 to 7, the method comprising:
(i) placing a plurality of balancers (12) for collecting water samples on a fixed carrier (11), connecting the balancers to the vacuumizing main pipeline (33) through respective independent gas pipelines, and opening electromagnetic valves in the control panel module (14) to enable the gas pipelines of the balancers (12) to be communicated with the vacuumizing main pipeline;
(ii) vacuumizing each balancer (12) and pipeline in the balancing unit (1) to a preset vacuum degree, introducing standard carbon dioxide into the balancers (12), stopping introducing the standard carbon dioxide after the pressure of each balancer (12) reaches a preset pressure, closing an electromagnetic valve in a control panel module, keeping the gas pipeline of each balancer and the vacuumizing main pipeline in a disconnected state for 2-5 minutes, and controlling the fixed carrier frame (11) and the balancers (12) to synchronously reciprocate in the heat treatment device (13) along the horizontal direction to perform carbon dioxide-water balance exchange of carbon dioxide and oxygen in water;
(iii) after the carbon dioxide-water balance exchange in the step (ii) is finished, vacuumizing a primary cold trap (21), a secondary cold trap (22) and each sample collecting pipe (23) in the sample collecting unit (2) to a preset vacuum degree, respectively freezing the primary cold trap (21), the secondary cold trap (22) and the sample collecting pipe (23) by using refrigeration devices filled with cold liquids with different temperatures, then controlling an independent gas pipeline at the top of a balancer (12) to sequentially release carbon dioxide obtained after the carbon dioxide-water balance exchange, sequentially removing moisture and organic hydrocarbon gas from the carbon dioxide obtained after the carbon dioxide-water balance exchange by the primary cold trap (21) and the secondary cold trap (22), and purifying the carbon dioxide obtained after the carbon dioxide-water balance exchange, then the purified carbon dioxide is sequentially frozen and collected through each sample collecting pipe (23);
(iv) and completely collecting the carbon dioxide obtained after the carbon dioxide-water balance exchange, taking down the sample collecting pipes (23) one by one, connecting the sample collecting pipes to a sample inlet of an oxygen isotope analysis instrument, releasing the carbon dioxide in the sample collecting pipes (23), and carrying out oxygen isotope analysis to obtain the oxygen isotope ratio in the carbon dioxide.
9. The method for performing isotopic analysis of oxygen in water according to claim 8, wherein in step (ii), each of said balancers (12) and pipes in said balancing unit (1) is evacuated to a vacuum level of 0.1 torr or more; introducing standard carbon dioxide into the balancer (12) until the pressure of the balancer (12) reaches 450 and 550 torr; the conditions for carbon dioxide-water equilibrium exchange of carbon dioxide with oxygen in water include: controlling the temperature of the heat treatment device (13) to be 20-30 ℃ and the carbon dioxide-water balance exchange time to be 2.5-4 hours; and vacuumizing the primary cold trap (21), the secondary cold trap (22) and each sample collecting pipe (23) in the sample collecting unit (2) until the vacuum degree reaches more than 0.1 torr.
10. The method for performing the underwater oxygen isotope analysis of claim 8, wherein in the step (iv), before the sample collection pipe opening on the side wall of the sample collection pipe (23) is connected to the sample inlet of the oxygen isotope analysis instrument, the method further comprises opening a heating element switch in the extraction system to heat each pipeline in the balancing unit (1) and the sample collection unit (2).
11. The method for performing isotopic analysis of oxygen in water according to claim 10, wherein in step (iv) each line in said equilibration unit (1) and sample collection unit (2) is heated to 40-60 ℃.
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| CN104181022A (en) * | 2014-08-28 | 2014-12-03 | 中国科学院地质与地球物理研究所 | System and method for preparing carbon dioxide gas needed by carbonate coupled isotope analysis |
| CN107422024A (en) * | 2017-08-03 | 2017-12-01 | 核工业北京地质研究院 | The analysis system and method for not oxygen-containing mineral inclusion water oxygen isotopics |
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| CN104181022A (en) * | 2014-08-28 | 2014-12-03 | 中国科学院地质与地球物理研究所 | System and method for preparing carbon dioxide gas needed by carbonate coupled isotope analysis |
| CN107422024A (en) * | 2017-08-03 | 2017-12-01 | 核工业北京地质研究院 | The analysis system and method for not oxygen-containing mineral inclusion water oxygen isotopics |
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