CN109856308B - Method and device for analyzing nitrogen-oxygen isotope composition - Google Patents
Method and device for analyzing nitrogen-oxygen isotope composition Download PDFInfo
- Publication number
- CN109856308B CN109856308B CN201910257291.5A CN201910257291A CN109856308B CN 109856308 B CN109856308 B CN 109856308B CN 201910257291 A CN201910257291 A CN 201910257291A CN 109856308 B CN109856308 B CN 109856308B
- Authority
- CN
- China
- Prior art keywords
- gas
- purification
- chromatographic column
- separation
- trap
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 196
- 238000000746 purification Methods 0.000 claims abstract description 90
- 238000000926 separation method Methods 0.000 claims abstract description 67
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 238000005336 cracking Methods 0.000 claims abstract description 17
- 238000004817 gas chromatography Methods 0.000 claims abstract description 16
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- 229910002651 NO3 Inorganic materials 0.000 claims description 25
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 25
- 239000012855 volatile organic compound Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 229920000557 Nafion® Polymers 0.000 claims description 16
- 239000010425 asbestos Substances 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 239000010431 corundum Substances 0.000 claims description 15
- 229910052895 riebeckite Inorganic materials 0.000 claims description 15
- 230000001580 bacterial effect Effects 0.000 claims description 12
- 238000013375 chromatographic separation Methods 0.000 claims description 12
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 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 7
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000003883 substance clean up Methods 0.000 claims description 4
- 239000012629 purifying agent Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 21
- 238000004458 analytical method Methods 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 5
- 239000001307 helium Substances 0.000 description 21
- 229910052734 helium Inorganic materials 0.000 description 21
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 16
- 239000012159 carrier gas Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000002457 bidirectional effect Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
Abstract
The invention relates to the technical field of stable isotope analysis, in particular to a method and a device for analyzing nitrogen-oxygen isotope composition. The invention contains N 2 After the O mixed gas is subjected to first separation and purification, the N-containing gas can be primarily removed 2 Impurity gas in the O mixed gas; then the mixture is separated by gas chromatography and then is heated and decomposed, so that N in the system can be realized 2 Cracking of O to O with separation from residual impurity gases 2 And N 2 The problem that the accuracy of the test result is affected by oxygen isotope exchange is avoided, and delta is accurately measured 15 N、δ 17 O and delta 18 O lays a foundation; then thoroughly removing or separating residual impurity gas in the system through second separation and purification; finally realizing delta by isotope mass spectrometry 15 N、δ 17 O and delta 18 And (3) measuring O. Experimental results of the examples show that delta can be obtained simultaneously by the method provided by the invention 15 N、δ 17 O and delta 18 The value of O, and the data accuracy and stability are good.
Description
Technical Field
The invention relates to the technical field of stable isotope analysis, in particular to a method and a device for analyzing nitrogen-oxygen isotope composition.
Background
Nitrogen and oxygen isotopes are widely used in research of water circles, rock circles, biospheres and atmospheric circles, nitrate is one of important substances in nitrogen circulation research, and nitrate from different sources has different nitrogen and oxygen isotope compositions, so that the composition of the nitrogen and oxygen isotopes can be used for distinguishing the sources, migration and conversion of the nitrate, and further tracing the nitrogen circulation process. In recent years, nitrogen-oxygen isotope analysis technology is also continuously advanced, and the traditional wet chemical method, vacuum pyrolysis method, and the recent cadmium reduction method and bacterial denitrification method are changed, so that the analysis method is more effective, rapid and convenient, and can meet the development research direction of nitrate.
At present, the prior art adopts a bacterial denitrification method to carry out NO 3 - Conversion to N 2 O gas, which converts all gases generated in the denitrification process (including N 2 O, volatile organic gas, CO 2 And water vapor, etc.), concentrating, separating and purifying with magnesium perchlorate and caustic soda asbestos and enrichment and purification cold trap and gas chromatography, and purifying the obtained purified N 2 Mass spectrometry is carried out on O gas to obtain delta 15 N and delta 18 O value. The method has the advantages of simple and convenient operation, rapidness and small sample consumption, but only can obtain delta at the same time 15 N and delta 18 O values are not sufficient to accurately determine the source, migration and conversion of nitrate.
Disclosure of Invention
The invention aims to provide a method and a device for analyzing the composition of nitrogen-oxygen isotopes, and delta in a nitrate sample can be obtained simultaneously by adopting the method 15 N、δ 17 O and delta 18 The value of O, and the data accuracy and stability are good.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for analyzing the composition of nitrogen-oxygen isotopes, which comprises the following steps:
(1) Providing a solution containing N 2 An O mixed gas containing N 2 The mixed gas of O is prepared from a nitrate sample by a bacterial denitrification method;
(2) The step (1) contains N 2 The mixed gas of O is subjected to first separation and purification to obtain N-containing gas 2 Purifying gas by O;
(3) The step (2) contains N 2 Separating O purified gas by gas chromatography, and performing thermal decomposition in the presence of catalyst to obtain O-containing gas 2 And N 2 Mixing the gases;
(4) Will be spentO is contained in the step (3) 2 And N 2 The mixed gas is subjected to secondary separation and purification to obtain purified O 2 And N 2 ；
(5) Purifying O in said step (4) 2 And N 2 Performing isotope mass spectrometry analysis to obtain the nitrogen-oxygen isotope composition of a nitrate sample, wherein the nitrogen-oxygen isotope comprises delta 15 N、δ 17 O and delta 18 O。
Preferably, the first separation and purification in the step (2) includes pre-purification, volatile organic compound purification, first enrichment and purification treatment, gas chromatography separation and second enrichment and purification treatment which are sequentially performed; the purification reagents used for the pre-purification include magnesium perchlorate and caustic soda asbestos.
Preferably, the chromatographic column used for the gas chromatographic separation in the step (3) is a PoraPLOT Q chromatographic column, the granularity of the packing in the chromatographic column is 50-80 meshes, and the length of the chromatographic column is 25-35 m.
Preferably, the catalyst in step (3) comprises platinum; the temperature of the thermal decomposition is 800-1000 ℃.
Preferably, the second separation and purification in the step (4) comprises gas chromatography separation and final purification which are sequentially performed; the purification device used for the final purification comprises a Nafion water trap.
Preferably, the chromatographic column used for gas chromatographic separation in the second separation and purification isThe length of the molecular sieve chromatographic column is 25-35 m, and the outer diameter of the molecular sieve chromatographic column is 0.53mm.
The invention provides a device for analyzing the composition of nitrogen-oxygen isotopes, which comprises
A first gas purification and separation device 2;
the gas cracking-separating and purifying device 3, wherein the gas cracking-separating and purifying device 3 comprises a second chromatographic column 8, a corundum platinum pipe cracking furnace 14 and a second gas purifying and separating device which are sequentially communicated; wherein the second chromatographic column 8 is connected with the first gas purification and separation device 2;
and a gas isotope mass spectrometer 4 communicated with the second gas purification and separation device.
Preferably, the first gas purification and separation device 2 comprises a magnesium perchlorate-caustic soda asbestos trap 12, a volatile organic compound trap 13, a first cold trap 10, a first chromatographic column 7, a second cold trap 11, a first six-way valve 5 and a second six-way valve 6;
wherein the air outlet of the magnesium perchlorate-caustic soda asbestos trap 12 is communicated with the air inlet of the volatile organic compound trap 13 through a pipeline;
the first six-way valve 5 comprises 6 pipeline ports, wherein 4 pipeline ports are respectively connected with an air outlet pipeline of the volatile organic compound trap 13, an air inlet pipeline of the first cold trap 10, an air outlet pipeline of the first cold trap 10 and an air inlet pipeline of the first chromatographic column 7;
the second six-way valve 6 comprises 6 pipeline ports, wherein 4 pipeline ports are respectively connected with an air outlet pipeline of the first chromatographic column 7, an air inlet pipeline of the second cold trap 11, an air outlet pipeline of the second cold trap 11 and an air inlet pipeline of the second chromatographic column 8.
Preferably, the second gas purification and separation device comprises a third chromatographic column 9 and a Nafion dehydration trap 15 which are sequentially communicated, wherein the third chromatographic column 9 is communicated with the corundum platinum pipe cracking furnace 14, and the Nafion dehydration trap 15 is communicated with the gas isotope mass spectrometer 4.
Preferably, the gas purifying and separating device further comprises an automatic sampler 1, wherein the automatic sampler 1 is communicated with the gas inlet end of the first gas purifying and separating device 2.
The invention provides a method for analyzing the composition of nitrogen-oxygen isotopes, which comprises the following steps: (1) Providing a solution containing N 2 An O mixed gas containing N 2 The mixed gas of O is prepared from a nitrate sample by a bacterial denitrification method; (2) The step (1) contains N 2 The mixed gas of O is subjected to first separation and purification to obtain N-containing gas 2 Purifying gas by O; (3) The step (2) contains N 2 Separating O purified gas by gas chromatography, and performing thermal decomposition in the presence of catalyst to obtain O-containing gas 2 And N 2 Mixing the gases; (4) The O in the step (3) is contained 2 And N 2 The mixed gas is subjected to secondary separation and purification to obtain purified O 2 And N 2 The method comprises the steps of carrying out a first treatment on the surface of the (5) Purifying O in said step (4) 2 And N 2 Performing isotope mass spectrometry analysis to obtain the composition of nitrogen and oxygen isotopes in the nitrate sample, wherein the nitrogen and oxygen isotopes comprise delta 15 N、δ 17 O and delta 18 O. The invention contains N 2 After the O mixed gas is subjected to first separation and purification, the N-containing gas can be primarily removed 2 Impurity gas in the O mixed gas; then the mixture is separated by gas chromatography and then is heated and decomposed, so that N in the system can be realized 2 Cracking of O to O with separation from residual impurity gases 2 And N 2 The problem that the accuracy of the test result is affected by oxygen isotope exchange is avoided, and delta is accurately measured 15 N、δ 17 O and delta 18 O lays a foundation; then thoroughly removing or separating residual impurity gas in the system through second separation and purification; finally realizing delta by isotope mass spectrometry 15 N、δ 17 O and delta 18 And (3) measuring O. Experimental results of the examples show that delta can be obtained simultaneously by the method provided by the invention 15 N、δ 17 O and delta 18 The value of O, and the data accuracy and stability are good.
Drawings
FIG. 1 is a schematic diagram of a device for analyzing the composition of nitrogen and oxygen isotopes;
FIG. 2 is a schematic view of a "LOAD" mode in an apparatus for analyzing the composition of nitrogen and oxygen isotopes provided by the present invention;
FIG. 3 is a schematic view of a "TRANSFER" mode in the apparatus for analyzing nitrogen and oxygen isotope composition provided by the present invention;
FIG. 4 is a schematic view of a "MEASURE" model in the apparatus for analyzing nitrogen and oxygen isotope composition provided by the present invention;
wherein 1 is an automatic sampler, 2 is a first gas purification and separation device, 3 is a gas cracking-separation and purification device, 4 is a gas isotope mass spectrometer, 5 is a first six-way valve and 6 is a second six-way valve, 5-1 to 5-6 and 6-1 to 6-6 are pipe ports of the first six-way valve and the second six-way valve respectively, 7 is a first chromatographic column, 8 is a second chromatographic column, 9 is a third chromatographic column, 10 is a first cold trap, 11 is a second cold trap, 12 is a magnesium perchlorate-caustic soda asbestos trap, 13 is a volatile organic compound trap, 14 is a corundum platinum pipe cracking furnace, 15 is a Nafion dehydration trap, and 16-1 to 16-4 are carrier gas devices.
Detailed Description
The invention provides a method for analyzing the composition of nitrogen-oxygen isotopes, which comprises the following steps:
(1) Providing a solution containing N 2 An O mixed gas containing N 2 The mixed gas of O is prepared from a nitrate sample by a bacterial denitrification method;
(2) The step (1) contains N 2 The mixed gas of O is subjected to first separation and purification to obtain N-containing gas 2 Purifying gas by O;
(3) The step (2) contains N 2 Separating O purified gas by gas chromatography, and performing thermal decomposition in the presence of catalyst to obtain O-containing gas 2 And N 2 Mixing the gases;
(4) The O in the step (3) is contained 2 And N 2 The mixed gas is subjected to secondary separation and purification to obtain purified O 2 And N 2 ；
(5) Purifying O in said step (4) 2 And N 2 Performing isotope mass spectrometry analysis to obtain the nitrogen-oxygen isotope composition of a nitrate sample, wherein the nitrogen-oxygen isotope comprises delta 15 N、δ 17 O and delta 18 O。
The invention provides a N-containing alloy 2 An O mixed gas containing N 2 The mixed gas of O is prepared from nitrate samples by a bacterial denitrification method. In the invention, the nitrate sample is treated by bacterial denitrification to obtain the N-containing sample 2 The O mixture gas comprises N 2 In addition to O, the catalyst also comprises volatile organic compounds and CO 2 And impurity gases such as water vapor.
The source of the nitrate sample is not particularly limited, and nitrate samples well known to those skilled in the art can be used; in the embodiment of the invention, in order to verify the accuracy of the method provided by the invention, nitrogen and oxygen isotope international standard substances USGS32, USGS34, USGS35 and IAEA-NO-3 are specifically adopted. The specific operation steps and parameters of the bacterial denitrification method are not particularly limited, and technical schemes well known to those skilled in the art can be adopted.
Obtaining N-containing 2 After O is mixed with the gas, the invention leads the gas containing N 2 The mixed gas of O is subjected to first separation and purification to obtain N-containing gas 2 O purified gas. In the present invention, the whole process from the first separation and purification to the isotope mass spectrometry is preferably performed in the presence of a carrier gas, preferably helium.
In the present invention, the first separation and purification preferably includes pre-purification, volatile organic compound purification, first enrichment and purification treatment, gas chromatography separation, and second enrichment and purification treatment, which are sequentially performed; the purification reagents used for the pre-purification preferably comprise magnesium perchlorate and caustic soda asbestos. In the present invention, the N-containing 2 And concentrating and removing impurities from the O purified gas through the first separation and purification.
In the present invention, the preliminary purification in the first separation and purification can remove the N-containing 2 Most of CO in O mixed gas 2 And water vapor. In the invention, the mass ratio of the magnesium perchlorate to the caustic soda asbestos in the purifying reagent used for the pre-purification is preferably 1: (2-3).
In the invention, the volatile organic compound purification in the first separation and purification can remove most of volatile organic compounds in the system. In the present invention, the device used for purifying the volatile organic compound is preferably a SUPELCO brand F well (SUPELCO Trap F).
In the invention, the first enrichment and purification treatment in the first separation and purification can realize enrichment and purification of the mixed gas, and is convenient for subsequent gas chromatographic separation. In the present invention, the apparatus used for the first enrichment and purification process is preferably a cold trap; the cold trap is not particularly limited, and cold traps well known to those skilled in the art, such as stainless steel tubes, may be used.
In the present invention, the gas chromatography separation in the first separation and purification can separate N in the system 2 O andand the residual small amount of impurity gas is separated, so that the subsequent second enrichment and purification treatment is facilitated. In the present invention, the chromatographic column used for the gas chromatographic separation is preferably a poraPLOT Q chromatographic column, the particle size of the packing in the chromatographic column is preferably 50-80 meshes, and the length of the chromatographic column is preferably 25-35 m.
In the invention, the second enrichment and purification treatment in the first separation and purification can realize enrichment and purification of the mixed gas, and is convenient for subsequent gas chromatographic separation and thermal decomposition treatment. In the present invention, the apparatus used for the second enrichment and purification treatment is preferably a cold trap; the cold trap is not particularly limited, and cold traps well known to those skilled in the art can be used, such as stainless steel tubes with internally nested fused silica capillaries of 0.32mm diameter.
In the invention, after the first separation and purification, volatile organic compounds, water vapor and most of CO in the system 2 Is removed to obtain N-containing 2 O purification gas except N 2 Contains a trace amount of CO in addition to O 2 。
Obtaining N-containing 2 After purifying the gas, the invention purifies the gas containing N 2 Separating O purified gas by gas chromatography, and performing thermal decomposition in the presence of catalyst to obtain O-containing gas 2 And N 2 And (3) mixing the gases. In the present invention, the chromatographic column used for the gas chromatographic separation is preferably a poraPLOT Q chromatographic column, the particle size of the packing in the chromatographic column is preferably 50-80 meshes, and the length of the chromatographic column is preferably 25-35 m. In the present invention, the catalyst preferably comprises platinum; the temperature of the thermal decomposition is preferably 800 to 1000 ℃. The invention realizes N-containing through gas chromatographic separation 2 N in O purified gas 2 O and CO 2 Wherein CO 2 Prior to N 2 O passes through the chromatographic column and CO 2 Stable in properties, and can not be cracked in the subsequent thermal decomposition process, while N 2 O is completely cleaved into O 2 And N 2 The method comprises the steps of carrying out a first treatment on the surface of the If gas chromatographic separation is not advanced, N 2 O and CO 2 While in a heating environment, CO 2 Will be in contact with N 2 O from cleavage of O 2 Isotope productionExchange (e.g. C) 18 O 16 O+ 16 O 16 O→C 16 O 16 O+ 18 O 16 O), affecting the accuracy of the test results.
In the present invention, after the thermal decomposition, the obtained O-containing material 2 And N 2 The mixed gas contains O 2 And N 2 In addition to trace amounts of CO 2 (wherein the trace amount of CO 2 Will be earlier than O 2 And N 2 Through the equipment used for thermal decomposition and subsequent second separation and purification).
Obtaining the O-containing 2 And N 2 After mixing the gases, the invention leads the gas containing O to 2 And N 2 The mixed gas is subjected to secondary separation and purification to obtain purified O 2 And N 2 . In the present invention, the second separation and purification preferably includes gas chromatography separation and final purification which are sequentially performed. In the present invention, the O-containing 2 And N 2 The mixed gas is further separated and purified through the second separation and purification.
In the present invention, the column used for the gas chromatography in the second separation and purification is preferablyThe length of the molecular sieve chromatographic column is preferably 25-35 m, and the outer diameter is preferably 0.53mm. The invention realizes O in a system through the gas chromatographic separation 2 、N 2 And residual impurities (such as trace amounts of CO as described above 2 And trace water vapor and other impurities possibly remained in the system), and the separation and removal of the impurities can be conveniently realized through subsequent final purification.
In the present invention, the purification device used for the final purification preferably comprises a Nafion water trap. The invention removes trace water vapor possibly remained in the system through the Nafion dehydration trap.
In the invention, after the second separation and purification, the impurity gas in the system is removed or separated, and the obtained purified O 2 And N 2 Contains only O 2 And N 2 (wherein, the trace amount of CO 2 After further separation by gas chromatography in the second separation and purification, O is preceded 2 And N 2 Enters the device for isotope mass spectrometry analysis, and does not lead to final O 2 And N 2 The measurement results of (2) have an influence).
Obtaining the purified O 2 And N 2 The invention then provides the purified O 2 And N 2 Performing isotope mass spectrometry analysis to obtain the composition of nitrogen and oxygen isotopes in the nitrate sample, wherein the nitrogen and oxygen isotopes comprise delta 15 N、δ 17 O and delta 18 O. The present invention is not particularly limited to the isotope mass spectrometry, and may employ technical schemes well known to those skilled in the art.
The invention provides a device for analyzing the composition of nitrogen and oxygen isotopes, which is shown in figure 1 and comprises a first gas purifying and separating device 2;
the gas cracking-separating and purifying device 3, wherein the gas cracking-separating and purifying device 3 comprises a second chromatographic column 8, a corundum platinum pipe cracking furnace 14 and a second gas purifying and separating device which are sequentially communicated; wherein the second chromatographic column 8 is connected with the first gas purification and separation device 2;
and a gas isotope mass spectrometer 4 communicated with the second gas purification and separation device.
As an embodiment of the present invention, the first gas purification and separation device 2 includes a magnesium perchlorate-caustic soda asbestos trap 12, a volatile organic compound trap 13, a first cold trap 10, a first chromatographic column 7, a second cold trap 11, a first six-way valve 5 and a second six-way valve 6;
wherein the air outlet of the magnesium perchlorate-caustic soda asbestos trap 12 is communicated with the air inlet of the volatile organic compound trap 13 through a pipeline;
the first six-way valve 5 comprises 6 pipeline ports (pipeline ports 5-1 to 5-6), wherein 4 pipeline ports are respectively connected with an air outlet pipeline of the volatile organic compound trap 13, an air inlet pipeline of the first cold trap 10, an air outlet pipeline of the first cold trap 10 and an air inlet pipeline of the first chromatographic column 7;
the second six-way valve 6 comprises 6 pipeline ports (pipeline ports 6-1 to 6-6), wherein 4 pipeline ports are respectively connected with an air outlet pipeline of the first chromatographic column 7, an air inlet pipeline of the second cold trap 11, an air outlet pipeline of the second cold trap 11 and an air inlet pipeline of the second chromatographic column 8.
As an embodiment of the present invention, the remaining 2 pipe ports of the first six-way valve 5 and the second six-way valve 6 are a carrier gas inlet and an exhaust port.
The invention realizes the communication of the volatile organic compound trap 13, the first cold trap 10 and the gas circuit of the first chromatographic column 7 through the first six-way valve 5, and realizes the communication of the first chromatographic column 7, the second cold trap 11 and the gas circuit of the second chromatographic column 8 through the second six-way valve 6; the invention fully utilizes the switching function of the first six-way valve 5 and the second six-way valve 6, and realizes separation and purification by controlling the gas flow direction in the system. The manner of "switching" the first six-way valve 5 and the second six-way valve 6 and the specific distribution manner of the pipes connected to the respective pipe ports in the present invention will be described in detail later in connection with the use of the device.
As an embodiment of the present invention, the apparatus for analyzing the composition of nitrogen and oxygen isotopes further comprises an autosampler 1, wherein the autosampler 1 is in communication with the air inlet end of the first gas purification and separation apparatus 2, specifically the apparatus for analyzing the composition of nitrogen and oxygen isotopes comprises a gas containing N by the autosampler 1 2 The O-mixed gas is introduced into the magnesium perchlorate-caustic soda asbestos trap 12, and then the first gas purification and separation is started. As an embodiment of the present invention, the autosampler 1 includes a double-wire sampling needle and a sample bottle; the sample bottle is preferably a Labco bottle (12 mL), and compared with a common jaw bottle (20 mL), the sample bottle has smaller volume, lower background and easier blowing, has more advantages on trace samples, has smaller bacterial liquid amount and is reduced to 2mL from the conventional 4 mL.
As an embodiment of the invention, the corundum platinum pipe cracking furnace 14 is a non-porous corundum pipe cracking furnace with a built-in platinum pipe (wherein, the corundum pipe has an outer diameter of 1.55mm, an inner diameter of 0.8mm, a length of 320mm, and the platinum pipe has an outer diameter of 0.8mm and an inner diameter of 0.5 mm), and has the advantages of easy assembly and high decomposition efficiency.
As an embodiment of the present invention, the second gas purification and separation device comprises a third chromatographic column 9 and a Nafion water trap 15 which are sequentially communicated, wherein the third chromatographic column 9 is communicated with the corundum platinum pipe cracking furnace 14, and the Nafion water trap 15 is communicated with the gas isotope mass spectrometer 4. In one implementation of the present invention, an air inlet is arranged at the upper end of the Nafion water trap 15, and an air outlet is arranged at the lower end; the gas inlet is used for introducing helium to purge the Nafion dehydration trap, and the gas outlet is used for discharging helium and trace water vapor possibly remained in the system.
As an embodiment of the present invention, the gas isotope mass spectrometer 4 is a MAT253 gas isotope mass spectrometer.
As an embodiment of the present invention, the apparatus for analyzing the composition of nitrogen and oxygen isotopes further includes a carrier gas device (as shown in fig. 2 to 4, the carrier gas devices 16-1 to 16-4 shown in fig. 2 to 4 do not represent exact positions thereof, but are only for convenience of representing carrier gas flow rates) for supplying carrier gas; the position of the carrier gas device is not particularly limited, and the carrier gas device can be used for carrying out the required treatment on the gas in the carrying system.
The method for analyzing the nitrogen-oxygen isotope by adopting the device for analyzing the nitrogen-oxygen isotope composition provided by the invention for analyzing the nitrogen-oxygen isotope of the nitrate sample preferably comprises the following steps:
the double-line sample injection needle is inserted into a sample bottle, a carrier gas device (specifically helium is taken as carrier gas, the carrier gas devices 16-1 to 16-4 are expressed as He 16-1 to 16-4), the flow rate of He 16-1 is controlled to be 30mL/min, and the nitrate sample is prepared into the N-containing sample by a bacterial denitrification method 2 O-gas mixture (including N 2 O and organic gas, CO 2 And water vapor) is introduced into the magnesium perchlorate-caustic soda asbestos trap 12 to remove most of the CO 2 And moisture, and then introduced into the volatile organic compound trap 13 to remove most of the volatile organic compounds.
The first six-way valve 5 is set to be in the "LOAD" mode (as shown in FIG. 2) while controlling the flow rate of He16-2>The pipeline at the two ends is closed after 20s of the pipeline at the two ends are purged in a two-way manner at 100 mL/min; after the two-wire injection needle was inserted into the sample bottle for 20s, the first cold trap 10 was immersed in a liquid nitrogen tank (in this process, containing N 2 The O mixed gas is carried by helium gas and is fed in from a pipeline port 5-6 and discharged out from a pipeline port 5-5 of a first six-way valve 5, so that liquid nitrogen is injectedThe frozen gas is frozen in the first cold trap 10, other impurity gases are blown away by the inlet of the pipeline opening 5-2 and the outlet of the pipeline opening 5-1 under the carrying of helium gas, after 10min, the sample injection needle is pulled out, the first cold trap 10 is lifted from the liquid nitrogen barrel, the first six-way valve 5 is switched into a TRANSFER mode (shown in figure 3) immediately, and meanwhile, the flow of He16-2 is controlled>And (3) the flow rate is 100mL/min, and the pipelines at the two ends are closed after 20s of bidirectional purging. The flow rate of He 16-3 is controlled to be about 5mL/min, helium enters through the pipe joint 5-3 of the first six-way valve 5 and exits through the pipe joint 5-2, and the gas (comprising N 2 O、CO 2 And volatile organic gas) is carried by helium gas, enters from a pipeline port 5-5 of a first six-way valve 5 and exits from a pipeline port 5-4, passes through a first chromatographic column 7 (a PoraPLOT Q chromatographic column, the granularity of packing is 50-80 meshes, the length is 25-35 m, and the column temperature is 25 ℃), and when a first cold trap 10 is lifted from a liquid nitrogen barrel for 120 seconds, a second cold trap 11 is immersed into the liquid nitrogen barrel (in the process, the system contains a small amount of N of impurity gas) 2 O gas is carried by helium gas and is fed in from a pipeline port 6-5 and discharged from a pipeline port 6-4 of the second six-way valve 6, the gas which can be frozen by liquid nitrogen is frozen in a second cold trap 11, other impurity gas is fed in from a pipeline port 6-1 and discharged from a pipeline port 6-6 and is blown away under the carrying of the helium gas, after 260s, the second six-way valve 6 is switched into a MEASURE mode (shown in figure 4), and N is at the moment 2 O and trace CO 2 The volatile organic gas is completely passed through the first chromatographic column 7 and transferred into the second cold trap 11, but the volatile organic gas does not pass through the first chromatographic column 7 to reach the second cold trap 11, and the volatile organic gas passes through the first chromatographic column 7 and is blown away through the pipeline port 6-5 and the pipeline port 6-6 of the second six-way valve 6, thereby realizing the separation of the target gas N 2 O and the residual small amount of volatile organic gas.
When the second six-way valve 6 is switched to the 'measurement' mode, the flow rate of the He 16-4 is controlled to be about 10mL/min to carry out reverse purging so as to discharge any residual gas which can not be frozen by the second cold trap 11; after 4min, the second cold trap 11 is lifted from the liquid nitrogen barrel, N 2 O and trace CO 2 Is carried by helium gas and enters from a pipeline port 6-3 and a pipeline port 6-4 of a second six-way valve 6, and gas in a second cold trap 11 enters into a second color after being carried by helium gas and enters from a pipeline port 6-1 and a pipeline port 6-2The chromatographic column 8 (PoraPLOT Q chromatographic column, filler particle size of 50-80 meshes, length of 25-35 m, column temperature of 25 ℃) is separated by a second chromatographic column 8, and CO 2 Prior to N 2 O enters a corundum platinum pipe cracking furnace 14 at 800-1000 ℃ and then enters N of the corundum platinum pipe cracking furnace 14 2 O is completely cracked into O under the condition of 800-1000 DEG C 2 And N 2 (due to CO 2 Prior to N 2 O enters a corundum platinum pipe cracking furnace 14 at 800 ℃ and further generates O before cracking 2 And N 2 Enters the third chromatographic column 9, the Nafion water trap 15 and the gas isotope mass spectrometer 4, so that no opportunity and O exist 2 Isotope exchange reactions occur and will not be specific to the final O 2 And N 2 Influence of the measurement results of (2) O 2 And N 2 Sequentially passing through a third chromatographic column 9%Molecular sieve chromatographic column with length of 25-35 m, outer diameter of 0.53mm and column temperature of 35 deg.c to realize O 2 、N 2 And further separating the residual impurities, then sequentially introducing into a Nafion water trap 15, and purifying O 2 And N 2 Sequentially enter a gas isotope mass spectrometer 4 (MAT 253 gas isotope mass spectrometer) for delta 18 O、δ 17 O and delta 15 And (3) measuring N.
Before the mass spectrum is measured, the first six-way valve 5 and the second six-way valve 6 are switched to prepare for testing of the next sample.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The method for performing nitrogen-oxygen isotope analysis on the nitrate sample by adopting the device for analyzing the nitrogen-oxygen isotope composition (shown in the figure 1) provided by the invention comprises the following steps:
the double-line sample injection needle is inserted into a sample bottle, a carrier gas device (specifically helium is taken as carrier gas, the carrier gas devices 16-1 to 16-4 are expressed as He 16-1 to 16-4), the flow rate of He 16-1 is controlled to be 30mL/min, and the nitrate sample is prepared into the N-containing sample by a bacterial denitrification method 2 O-gas mixture (including N 2 O and organic gas, CO 2 And water vapor) is introduced into the magnesium perchlorate-caustic soda asbestos trap 12 to remove most of the CO 2 And moisture, and then introduced into the volatile organic compound trap 13 to remove most of the volatile organic compounds.
The first six-way valve 5 is set to be in the "LOAD" mode (as shown in FIG. 2) while controlling the flow rate of He16-2>The pipeline at the two ends is closed after 20s of the pipeline at the two ends are purged in a two-way manner at 100 mL/min; after the two-wire injection needle was inserted into the sample bottle for 20s, the first cold trap 10 was immersed in a liquid nitrogen tank (in this process, containing N 2 The O mixed gas is carried by helium and is fed into the pipeline mouth 5-6 and discharged from the pipeline mouth 5-5 of the first six-way valve 5, the gas which can be frozen by liquid nitrogen is frozen in the first cold trap 10, other impurity gases are fed into the pipeline mouth 5-2 and discharged from the pipeline mouth 5-1 and blown away under the carrying of helium), after 10min, the sample injection needle is pulled out, the first cold trap 10 is lifted from the liquid nitrogen barrel, the first six-way valve 5 is immediately switched into a TRANSFER mode (shown in figure 3), and meanwhile, the flow of He16-2 is controlled>And (3) the flow rate is 100mL/min, and the pipelines at the two ends are closed after 20s of bidirectional purging. The flow rate of He 16-3 is controlled to be about 5mL/min, helium enters through the pipe joint 5-3 of the first six-way valve 5 and exits through the pipe joint 5-2, and the gas (comprising N 2 O、CO 2 And volatile organic gas) is carried by helium gas, enters from a pipeline port 5-5 of a first six-way valve 5 and exits from a pipeline port 5-4, and passes through a first chromatographic column 7 (a PoraPLOT Q chromatographic column, the granularity of filler is 50-80 meshes, the length is 30m, and the column temperature is 25 ℃), when a first cold trap 10 is lifted from a liquid nitrogen barrel for 120 seconds, a second cold trap 11 is immersed into the liquid nitrogen barrel (in the process, N containing a small amount of impurity gas in the system is immersed into the liquid nitrogen barrel) 2 O gas is carried by helium gas and is fed in from a pipeline port 6-5 and discharged from a pipeline port 6-4 of the second six-way valve 6, the gas which can be frozen by liquid nitrogen is frozen in a second cold trap 11, other impurity gases are fed in from a pipeline port 6-1 and discharged from a pipeline port 6-6 and blown away under the carrying of the helium gas), and after 260s, the second six-way valve 6 is switchedIn "MEASURE" mode (as shown in FIG. 4), where N 2 O and trace CO 2 The volatile organic gas is completely passed through the first chromatographic column 7 and transferred into the second cold trap 11, but the volatile organic gas does not pass through the first chromatographic column 7 to reach the second cold trap 11, and the volatile organic gas passes through the first chromatographic column 7 and is blown away through the pipeline port 6-5 and the pipeline port 6-6 of the second six-way valve 6, thereby realizing the separation of the target gas N 2 O and the residual small amount of volatile organic gas.
When the second six-way valve 6 is switched to the 'measurement' mode, the flow rate of the He 16-4 is controlled to be about 10mL/min to carry out reverse purging so as to discharge any residual gas which can not be frozen by the second cold trap 11; after 4min, the second cold trap 11 is lifted from the liquid nitrogen barrel, N 2 O and trace CO 2 The gas carried by helium gas enters from a pipeline port 6-3 and exits from a pipeline port 6-4 of a second six-way valve 6, the gas in a second cold trap 11 enters into a second chromatographic column 8 (PortaPLOT Q chromatographic column, filler particle size is 50-80 meshes, length is 30m, column temperature is 25 ℃) after being carried by helium gas enters from a pipeline port 6-1 and exits from a pipeline port 6-2, and CO is separated by the second chromatographic column 8 2 Prior to N 2 O enters a corundum platinum pipe cracking furnace 14 at 800 ℃ and then enters N of the corundum platinum pipe cracking furnace 14 2 O is completely cleaved into O at 800 DEG C 2 And N 2 ，O 2 And N 2 Sequentially passing through a third chromatographic column 9%Molecular sieve chromatographic column with length of 30m, outer diameter of 0.53mm and column temperature of 35 ℃ to realize O 2 、N 2 And further separating the residual impurities, then sequentially introducing into a Nafion water trap 15, and purifying O 2 And N 2 Sequentially enter a gas isotope mass spectrometer 4 (MAT 253 gas isotope mass spectrometer) for delta 18 O、δ 17 O and delta 15 And (3) measuring N.
Before the mass spectrum is measured, the first six-way valve 5 and the second six-way valve 6 are switched to prepare for testing of the next sample.
The nitrate samples used in the method are nitrogen-oxygen isotope international standard substances USGS32, USGS34,USGS35 and IAEA-NO-3, delta 15 N、δ 18 O and delta 17 The true values of O are (180%o, 25.7%o, 13.4%o), (-1.8%o, -27.9%o, -14.8%o), (2.7%o, 57.5%o, 51.5%o), (4.7%o, 25.6%o, 13.2%o) respectively.
The experimental results of the analysis of the nitrate samples using the method described above are shown in table 1.
TABLE 1 results of Nitrogen-oxygen isotope analysis experiments
As can be seen from the data in Table 1, delta can be obtained simultaneously by the method provided by the invention 15 N、δ 17 O and delta 18 The value of O, and the data accuracy and stability are good.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A method of analyzing the composition of a nitrogen-oxygen isotope, comprising the steps of:
(1) Providing a solution containing N 2 An O mixed gas containing N 2 The mixed gas of O is prepared from a nitrate sample by a bacterial denitrification method;
(2) The step (1) contains N 2 The mixed gas of O is subjected to first separation and purification to obtain N-containing gas 2 Purifying gas by O; the first separation and purification in the step (2) comprises the steps of pre-purification, volatile organic compound purification, first enrichment and purification treatment, gas chromatography separation and second enrichment and purification treatment which are sequentially carried out; the purifying agent used for the pre-purification comprises magnesium perchlorate and caustic soda asbestos;
(3) The step (2) contains N 2 Separating O purified gas by gas chromatography, and performing thermal decomposition in the presence of catalyst to obtain O-containing gas 2 And N 2 Mixing the gases; the chromatographic column used in the gas chromatographic separation in the step (3) is a PoraPLOT Q chromatographic column, the granularity of the filler in the chromatographic column is 50-80 meshes, and the length of the chromatographic column is 25-35 m;
(4) The O in the step (3) is contained 2 And N 2 The mixed gas is subjected to secondary separation and purification to obtain purified O 2 And N 2 ；
(5) Purifying O in said step (4) 2 And N 2 Performing isotope mass spectrometry analysis to obtain the nitrogen-oxygen isotope composition of a nitrate sample, wherein the nitrogen-oxygen isotope comprises delta 15 N、δ 17 O and delta 18 O。
2. The method of claim 1, wherein the catalyst in step (3) comprises platinum; the temperature of the thermal decomposition is 800-1000 ℃.
3. The method of claim 1, wherein the second separation and purification in step (4) comprises gas chromatographic separation and final purification performed in sequence; the purification device used for the final purification comprises a Nafion water trap.
4. A method according to claim 3, wherein the chromatographic column used for the gas chromatographic separation isThe length of the molecular sieve chromatographic column is 25-35 m, and the outer diameter of the molecular sieve chromatographic column is 0.53mm.
5. An apparatus for analyzing the composition of nitrogen and oxygen isotopes, comprising
A first gas purification and separation device (2);
the gas cracking-separating and purifying device (3), wherein the gas cracking-separating and purifying device (3) comprises a second chromatographic column (8), a corundum platinum tube cracking furnace (14) and a second gas purifying and separating device which are sequentially communicated; wherein the second chromatographic column (8) is connected with the first gas purification and separation device (2);
a gas isotope mass spectrometer (4) in communication with the second gas purification and separation device;
the first gas purification and separation device (2) comprises a magnesium perchlorate-caustic soda asbestos trap (12), a volatile organic compound trap (13), a first cold trap (10), a first chromatographic column (7), a second cold trap (11), a first six-way valve (5) and a second six-way valve (6);
wherein the air outlet of the magnesium perchlorate-caustic soda asbestos trap (12) is communicated with the air inlet of the volatile organic compound trap (13) through a pipeline;
the first six-way valve (5) comprises 6 pipeline ports, wherein 4 pipeline ports are respectively connected with an air outlet pipeline of the volatile organic compound trap (13), an air inlet pipeline of the first cold trap (10), an air outlet pipeline of the first cold trap (10) and an air inlet pipeline of the first chromatographic column (7);
the second six-way valve (6) comprises 6 pipeline ports, wherein 4 pipeline ports are respectively connected with an air outlet pipeline of the first chromatographic column (7), an air inlet pipeline of the second cold trap (11), an air outlet pipeline of the second cold trap (11) and an air inlet pipeline of the second chromatographic column (8);
the second gas purification and separation device comprises a third chromatographic column (9) and a Nafion dehydration trap (15) which are sequentially communicated, wherein the third chromatographic column (9) is communicated with the corundum platinum tube cracking furnace (14), and the Nafion dehydration trap (15) is communicated with the gas isotope mass spectrometer (4);
the gas purification and separation device also comprises an automatic sampler (1), wherein the automatic sampler (1) is communicated with the gas inlet end of the first gas purification and separation device (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910257291.5A CN109856308B (en) | 2019-04-01 | 2019-04-01 | Method and device for analyzing nitrogen-oxygen isotope composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910257291.5A CN109856308B (en) | 2019-04-01 | 2019-04-01 | Method and device for analyzing nitrogen-oxygen isotope composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109856308A CN109856308A (en) | 2019-06-07 |
| CN109856308B true CN109856308B (en) | 2024-04-02 |
Family
ID=66902770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910257291.5A Active CN109856308B (en) | 2019-04-01 | 2019-04-01 | Method and device for analyzing nitrogen-oxygen isotope composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109856308B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111060610B (en) | 2019-12-06 | 2022-06-21 | 陕西科技大学 | Method for simultaneously determining nitrogen and oxygen isotope composition of natural nitrate and nitrite |
| CN111965282B (en) * | 2020-08-18 | 2023-08-29 | 中国地质科学院矿产资源研究所 | Ultra-trace sulfur isotope analysis system and analysis method |
| CN115290786B (en) * | 2022-08-03 | 2023-09-01 | 中国科学院广州地球化学研究所 | Method for analyzing oxygen exchange path in active oxygen reaction by combining isotope tracing technology and free radical capturing technology |
| CN115561349B (en) * | 2022-09-21 | 2023-08-18 | 中国地质科学院矿产资源研究所 | N (N) 2 Device and method for testing nitrogen and trioxyisotope of O gas and pyrolysis gas thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61213655A (en) * | 1985-03-19 | 1986-09-22 | Shimadzu Corp | Thermal analyzing instrument provided with gas chromatograph and mass spectrometer |
| JP2005083839A (en) * | 2003-09-05 | 2005-03-31 | Japan Science & Technology Agency | Method of measuring ratio of three kinds of stable oxygen isotopes in atmosphere or dissolved gas, and o2 isolation device used therefor |
| WO2012016624A1 (en) * | 2010-07-27 | 2012-02-09 | Elementar Analysensysteme Gmbh | Determination of the isotope ratios of carbon and nitrogen in water samples |
| CN103424462A (en) * | 2013-08-23 | 2013-12-04 | 中国科学院寒区旱区环境与工程研究所 | Enrichment analysis instrument of carbon and nitrogen of greenhouse gases of CO2 and N2O |
| CN104181247A (en) * | 2014-08-22 | 2014-12-03 | 中国科学院海洋研究所 | Measurement method of nitrogen and oxygen stable isotope of nitrate in seawater |
| CN104749278A (en) * | 2015-03-26 | 2015-07-01 | 中国科学院生态环境研究中心 | Method for determining N-DAMO (nitrite-dependent anaerobic methane oxidation) rate |
| CN105973671A (en) * | 2016-07-03 | 2016-09-28 | 中国科学院寒区旱区环境与工程研究所 | Nitrogen and oxygen isotope analyzer for nitrous oxide gas generated by denitrifying bacteria method |
| CN205786017U (en) * | 2016-07-03 | 2016-12-07 | 中国科学院寒区旱区环境与工程研究所 | Nitrous oxide gas nitrogen and oxygen isotopes analyzes front device |
| CN106404927A (en) * | 2016-07-03 | 2017-02-15 | 中国科学院寒区旱区环境与工程研究所 | A NO<3><->-<17>O isotope detection method for trace nitrates in ice cores |
| CN106745734A (en) * | 2016-12-02 | 2017-05-31 | 重庆大学 | A kind of method for analyzing single-stage biological nitrogen removal system nitrification and denitrification process nitrous oxide emission speed |
| CN108414633A (en) * | 2018-02-12 | 2018-08-17 | 中国科学院地质与地球物理研究所 | A kind of determining instrument of micro nitrogen isotope and its application |
| CN209927805U (en) * | 2019-04-01 | 2020-01-10 | 中国地质科学院矿产资源研究所 | Device for analyzing nitrogen-oxygen isotope composition |
-
2019
- 2019-04-01 CN CN201910257291.5A patent/CN109856308B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61213655A (en) * | 1985-03-19 | 1986-09-22 | Shimadzu Corp | Thermal analyzing instrument provided with gas chromatograph and mass spectrometer |
| JP2005083839A (en) * | 2003-09-05 | 2005-03-31 | Japan Science & Technology Agency | Method of measuring ratio of three kinds of stable oxygen isotopes in atmosphere or dissolved gas, and o2 isolation device used therefor |
| WO2012016624A1 (en) * | 2010-07-27 | 2012-02-09 | Elementar Analysensysteme Gmbh | Determination of the isotope ratios of carbon and nitrogen in water samples |
| CN103424462A (en) * | 2013-08-23 | 2013-12-04 | 中国科学院寒区旱区环境与工程研究所 | Enrichment analysis instrument of carbon and nitrogen of greenhouse gases of CO2 and N2O |
| CN104181247A (en) * | 2014-08-22 | 2014-12-03 | 中国科学院海洋研究所 | Measurement method of nitrogen and oxygen stable isotope of nitrate in seawater |
| CN104749278A (en) * | 2015-03-26 | 2015-07-01 | 中国科学院生态环境研究中心 | Method for determining N-DAMO (nitrite-dependent anaerobic methane oxidation) rate |
| CN105973671A (en) * | 2016-07-03 | 2016-09-28 | 中国科学院寒区旱区环境与工程研究所 | Nitrogen and oxygen isotope analyzer for nitrous oxide gas generated by denitrifying bacteria method |
| CN205786017U (en) * | 2016-07-03 | 2016-12-07 | 中国科学院寒区旱区环境与工程研究所 | Nitrous oxide gas nitrogen and oxygen isotopes analyzes front device |
| CN106404927A (en) * | 2016-07-03 | 2017-02-15 | 中国科学院寒区旱区环境与工程研究所 | A NO<3><->-<17>O isotope detection method for trace nitrates in ice cores |
| CN106745734A (en) * | 2016-12-02 | 2017-05-31 | 重庆大学 | A kind of method for analyzing single-stage biological nitrogen removal system nitrification and denitrification process nitrous oxide emission speed |
| CN108414633A (en) * | 2018-02-12 | 2018-08-17 | 中国科学院地质与地球物理研究所 | A kind of determining instrument of micro nitrogen isotope and its application |
| CN209927805U (en) * | 2019-04-01 | 2020-01-10 | 中国地质科学院矿产资源研究所 | Device for analyzing nitrogen-oxygen isotope composition |
Non-Patent Citations (1)
| Title |
|---|
| 土壤浸提液中硝酸盐氮氧同位素组成的反硝化细菌法测定;徐春英;李玉中;李巧珍;毛丽丽;林伟;强晓晶;郑欠;;农业环境科学学报(第09期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109856308A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109856308B (en) | Method and device for analyzing nitrogen-oxygen isotope composition | |
| CN209927805U (en) | Device for analyzing nitrogen-oxygen isotope composition | |
| KR100243882B1 (en) | Method of removing siloxanes from silicon compound gases and apparatus therefor and silloxane content analyzing apparatus | |
| CN101949906B (en) | Decompressed purge-and-trap processing equipment for non-volatile organic compound in water sample and processing method thereof | |
| CN111272917A (en) | Element isotope analysis system and method for analyzing sulfur isotope in trace sulfate sample and application thereof | |
| JP3482497B2 (en) | Isotope composition analyzer | |
| CN111551650A (en) | System and method for analyzing trace sulfur isotopes in sulfide and sulfate | |
| WO2021056943A1 (en) | System and method for purification, collection and preparation of isotope sample and use thereof | |
| US20080035840A1 (en) | Process and apparatus for isotope determination of condensed phase samples | |
| US5661038A (en) | Interface system for isotopic analysis of hydrogen | |
| CN112345667A (en) | Gaseous hydrocarbon preparation and online carbon isotope analysis device and method | |
| CN106404927A (en) | A NO<3><->-<17>O isotope detection method for trace nitrates in ice cores | |
| CN114609288A (en) | Silicate oxygen isotope testing system and method | |
| CN110579564B (en) | Device and method for simultaneously measuring mercury, cadmium, zinc and lead | |
| CN112540153A (en) | Device and method for extracting gaseous hydrocarbon hydrogen isotope composition in mineral inclusion | |
| CN108421280B (en) | Sulfhydrylation organic-inorganic hybrid monolithic column and preparation method and application thereof | |
| EP3234592B2 (en) | Isotope analysis | |
| CN208420815U (en) | For the gas chromatograph of methyl Mercury Determination in environmental and biological samples and inductively coupled plasma mass spectrometer coupling system | |
| JP3103985B2 (en) | Concentration analysis method and equipment | |
| JP2010122160A (en) | Mercury analyzing apparatus and method therefor | |
| CN215218715U (en) | Gaseous hydrocarbon isotope on-line extraction device in gas and mineral inclusion | |
| CN112255369A (en) | Online continuous flow analysis and extraction device and method for methane carbon isotope composition in gas | |
| CN106680405A (en) | Fully automatic air bag type sample feeding heat desorption analysis gas chromatography mass spectrometry method | |
| CN115047115B (en) | Equipment and method for testing oxygen isotope composition in low-oxygen-content sample | |
| CN108037236B (en) | Experimental device for collecting quantitative analysis gas of methane conversion rate in torch discharge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |