WO2025232129A1 - 一种Nano-C同位素分析装置 - Google Patents

一种Nano-C同位素分析装置

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Publication number
WO2025232129A1
WO2025232129A1 PCT/CN2024/131704 CN2024131704W WO2025232129A1 WO 2025232129 A1 WO2025232129 A1 WO 2025232129A1 CN 2024131704 W CN2024131704 W CN 2024131704W WO 2025232129 A1 WO2025232129 A1 WO 2025232129A1
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Prior art keywords
cold trap
way valve
isotope
freezing
port
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English (en)
French (fr)
Inventor
龚冰
査向平
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Priority to US19/019,977 priority Critical patent/US20250341491A1/en
Publication of WO2025232129A1 publication Critical patent/WO2025232129A1/zh
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • 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

Definitions

  • This invention belongs to the field of earth and planetary chemistry instrumentation technology, and particularly relates to a Nano-C isotope analysis device.
  • Carbon is not only one of the most abundant elements on Earth, but also a crucial element in the composition and evolution of carbon-based life.
  • Plate subduction provides the driving force for the carbon cycle within the Earth and on its surface (Dasguptae et al., 2004; Wang et al., 2014; Plank & Manning, 2019), and this carbon cycle has a significant impact on Earth's climate and surface habitability (Masone et al., 2017).
  • Utilizing carbon isotopes in natural geological samples can not only trace the source of materials in the carbon cycle but also the specific geological processes involved (Zheng et al., 2000; Galveze et al., 2013; Wang et al., 2014; Zhao et al., 2016; Plank & Manning, 2019). Therefore, accurately determining the carbon isotopic composition of natural geological samples is of great scientific significance for studying carbon within the Earth and the global carbon cycle.
  • Carbonate forms include compounds composed of carbonate and bicarbonate ions with different cations; non-carbonate forms are mainly elemental carbon (graphite, diamond, etc.).
  • Differences in carbon isotope composition can effectively distinguish the source of carbon, for example, differentiating between organic carbon (such as graphite, ⁇ 13C average -25 ⁇ ) and inorganic carbon (such as marine carbonates, ⁇ 13C average -0 ⁇ ).
  • Gasbench-MS is also an acid-dissolution method, mainly utilizing an online continuous flow analysis method (Gasbench-CF-IRMS, abbreviated as Gasbench-MS) connected to an isotope gas mass spectrometer (Brenna et al., 1997; Révész & Landwehr, 2002; Paul & Skrzypek, 2006). It is suitable for the analysis of small sample amounts of carbonates. Compared with the traditional phosphoric acid method, its advantages are higher analytical precision and a smaller sample volume required. It can accurately analyze the isotopic composition of carbon at the micromolar level (Révész & Landwehr, 2002; Paul & Skrzypek, 2006; Zha et al., 2010). It can analyze not only pure carbonates but also trace amounts of carbonates in silicates (Zha et al., 2010, 2018). However, the limitation of this method is that it cannot accurately determine samples with even lower carbon content, such as nanomolar levels of carbon.
  • EA-MS is a combustion oxidation method, primarily utilizing an online continuous flow analysis method that connects an elemental analyzer (combustion elemental analyzer) with an isotope gas mass spectrometer (Brenna et al., 1997; Werner et al., 1999). This method was initially applied to the analysis of carbon isotopes in organic samples, and has also been used to analyze the carbon isotope composition of natural geological samples (Zheng et al., 2000; Skrzypek & Paul, 2006; Zha et al., 2018).
  • trace amounts refers to samples where the content of the analyte is below the instrument's detection limit, making accurate determination impossible.
  • Micro-regions refers to direct in-situ analysis of the sample (e.g., using ion probes).
  • the "trace amount” technique also presents a bottleneck.
  • Zha et al. (2018) found that when using Gasbench-MS to analyze the carbon isotope composition of trace carbonates in silicates, the accuracy and precision of the analysis results were poor when the carbonate content was below 30 micrograms.
  • EA-MS to analyze the isotope composition of non-carbonate carbon in silicates, if the carbon content in the sample was below 500 ppm, even with optimized sample weighing, the analytical results remained far from ideal.
  • this invention proposes a Nano-C isotope analysis device that enables accurate determination of the isotopic composition of carbon in different forms at the nanomolar level in samples from Earth and extraterrestrial sources.
  • the present invention provides a Nano-C isotope analysis device, comprising an elemental analysis system, a carbon dioxide cryogenic enrichment system, and an isotope mass spectrometry analysis system connected in sequence.
  • the carbon dioxide cryogenic enrichment system includes a six-way valve connected to the elemental analysis system.
  • the six-way valve is connected to an independently configured first cryogenic component and a second cryogenic component.
  • the second port of the second cryogenic component is connected to the isotope mass spectrometry analysis system.
  • the first refrigeration assembly includes a first refrigeration container filled with refrigerant, and a first cold trap connected to the six-way valve is vertically and vertically disposed inside the first refrigeration container.
  • the second refrigeration component includes a second refrigeration container filled with refrigerant, and a second cold trap connected to the six-way valve is vertically and retractably installed inside the second refrigeration container.
  • the elemental analysis system includes an elemental analyzer, and the elemental analyzer is equipped with useful elements.
  • the reaction tube converts carbon elements in the raw material to be tested into gaseous carbon dioxide.
  • the second port of the reaction tube is connected to the six-way valve through a gas pipeline.
  • a first gas supply device for supplying high-speed carrier gas is provided on the gas pipeline.
  • a chemical trap is provided on the venting line, the chemical trap is located between the elemental analyzer and the six-way valve, the first port of the chemical trap is connected to the second port of the reaction tube, and the second port of the chemical trap is connected to the six-way valve.
  • the ventilation pipeline is provided with two independently configured branch pipes, and the two branch pipes are respectively provided with a first valve and a second valve.
  • the first valve is connected to an exhaust device for venting the carrier gas
  • the second valve is connected to a second gas supply device for supplying auxiliary carrier gas.
  • the second cold trap is separated from the second freezing container, the venting pipe is connected to the first port of the first cold trap through the six-way valve, and the second port of the first cold trap is connected to the venting pipe provided on the six-way valve through the six-way valve.
  • the first port of the second cold trap is connected to a third gas supply device through the six-way valve, and the second port of the second cold trap is connected to the isotope mass spectrometry analysis system.
  • the first cold trap is separated from the first freezing container to ensure that the carbon dioxide frozen and enriched in the first cold trap can be completely frozen and enriched in the second cold trap.
  • the venting pipe is connected to the venting pipe after passing through the six-way valve.
  • the third gas supply device is connected to the second port of the first cold trap through the six-way valve, and the first port of the second cold trap is connected to the first port of the second cold trap through the six-way valve.
  • the first cold trap is separate from the first freezing container and the second cold trap is separate from the first freezing container.
  • the carbon dioxide enriched in the second cold trap is vaporized and then fed into the isotope mass spectrometry analysis system by the low-speed carrier gas provided by the third gas supply device.
  • the isotope mass spectrometry analysis system includes a four-way valve connected to the second port of the second cold trap, and the second cold trap is connected to an isotope gas mass spectrometer through the four-way valve.
  • the isotope gas mass spectrometer is connected to the second port of the chemical trap via the four-way valve, and is directly connected to the elemental analyzer to achieve constant analysis.
  • This invention discloses a Nano-C isotope analysis device to solve the technical bottleneck of isotope analysis of trace amounts of carbon, achieving accurate determination of the isotopic composition of nanomolar carbon; after placing the sample to be tested into the elemental analysis system, the mixed air inside is purged to reduce the influence of airborne carbon on the analysis results; then, the carbon in the sample to be tested is converted into detectable carbon dioxide; the generated carbon dioxide enters the carbon dioxide cryogenic enrichment system for complete cryogenic enrichment, improving the sensitivity of the isotope mass spectrometry analysis system for carbon dioxide isotope mass spectrometry analysis; the first and second cryogenic components operate separately to achieve secondary enrichment and purification of carbon dioxide in the generated gas, avoiding inaccurate analysis results caused by carbon dioxide escape.
  • This method improves the analytical limit and enables nanomolar-level carbon isotope analysis.
  • the first cryogenic component is in operation, and the first cold trap is immersed in the cryogenic liquid in the first cryogenic container.
  • the mixed gas containing carbon dioxide is frozen in the first cold trap, while the remaining carrier gas is discharged through the six-way valve.
  • the second cryogenic enrichment of carbon dioxide the first cold trap is removed from the cryogenic liquid, and the second cryogenic liquid is immersed in the cryogenic liquid in the second cryogenic container.
  • the carbon dioxide liquefied in the first cold trap is heated and vaporized, then passes through the six-way valve and enters the second cold trap under low-flow-rate carrier gas for another cryogenic enrichment, thus improving analytical sensitivity.
  • the secondary cryogenic enrichment mainly utilizes the low-flow-rate carrier gas after the second cryogenic process to improve the sensitivity of mass spectrometry analysis, enabling accurate determination of the isotopic composition of different forms of carbon in samples from Earth and extraterrestrial sources at the nanomolar level.
  • the invention has a simple and compact structure, is easy to use, and can analyze carbon in different forms, achieving accurate determination of the isotopic composition of carbon in different forms at the nanomolar level.
  • Figure 1 is a schematic diagram of the Nano-C isotope analysis device of the present invention.
  • Figure 2 is a schematic diagram of the state during the first freezing separation of the carbon dioxide cryogenic enrichment system of the present invention
  • Figure 3 is a schematic diagram of the state during the second freezing separation of the carbon dioxide cryogenic enrichment system of the present invention
  • Figure 4 is a schematic diagram of the carbon dioxide discharge process of the carbon dioxide cryogenic enrichment system of the present invention.
  • Figure 5 shows the calibration and linearity graph of the Nano-C isotope analysis device of the present invention
  • Figure 6 is a precision analysis diagram of the Nano-C isotope analysis device of the present invention.
  • this embodiment provides a Nano-C isotope analysis device, including an elemental analysis system 1, a carbon dioxide cryogenic enrichment system 2, and an isotope mass spectrometry analysis system 3 connected in sequence.
  • the carbon dioxide cryogenic enrichment system 2 includes a six-way valve 21 connected to the elemental analysis system 1.
  • the six-way valve 21 is connected to an independently configured first cryogenic component and a second cryogenic component.
  • the second port of the second cryogenic component is connected to the isotope mass spectrometry analysis system 3.
  • the first refrigeration component includes a first refrigeration container 22 containing refrigerant, and a first cold trap 23 connected to a six-way valve 21 is vertically and vertically disposed inside the first refrigeration container 22.
  • the second refrigeration assembly includes a second refrigeration container 24 containing refrigerant, and a second cold trap 25 connected to a six-way valve 21 is vertically and vertically disposed inside the second refrigeration container 24.
  • This invention discloses a Nano-C isotope analysis device to overcome the technical bottleneck of isotope analysis of trace amounts of carbon, achieving accurate determination of the isotopic composition of nanomolar carbon.
  • the sample to be tested is placed in the elemental analysis system 1
  • the mixed air inside is purged to reduce the influence of airborne carbon on the analysis results.
  • the carbon in the sample is converted into detectable carbon dioxide.
  • the generated carbon dioxide enters the carbon dioxide cryogenic enrichment system 2 for complete cryogenic enrichment, facilitating isotope mass spectrometry analysis by the isotope mass spectrometry system 3.
  • the first and second cryogenic components operate separately to achieve secondary cryogenic enrichment of carbon dioxide in the generated gas, improving analytical sensitivity.
  • the first cryogenic component is in operation, and the first cold trap 23 is immersed in the low-temperature cryogenic liquid containing carbon dioxide in the first cryogenic container 22.
  • the carbon-containing gas mixture is cryogenically liquefied in the first cold trap 23, while the remaining carrier gas is discharged through the six-way valve 21.
  • the first cold trap 23 is removed from the cryogenic liquid, and the second cryogenic liquid is immersed in the cryogenic liquid in the second freezing container 24.
  • the carbon dioxide liquefied in the first cold trap 23 is heated and vaporized, then enters the second cold trap 25 through the six-way valve 21 under low-flow-rate carrier gas conditions for further cryogenic enrichment.
  • the secondary cryogenic purification process allows for adjustment of the carrier gas flow rate, facilitating subsequent mass spectrometry analysis under low-flow-rate carrier gas conditions, enabling accurate determination of the isotopic composition of different forms of carbon at the nanomolar level in samples from Earth and extraterrestrial environments.
  • This invention features a simple and compact mechanism, is easy to use, and can analyze carbon in different forms, achieving accurate determination of the isotopic composition of different forms of carbon at the nanomolar level.
  • cryogenic fluid is liquid nitrogen, dry ice, etc.
  • cryogenic fluid is liquid nitrogen, which can provide a cryogenic freezing temperature of -196°C.
  • a chemical trap 13 is installed on the ventilation pipeline 26.
  • the chemical trap 13 is located between the elemental analyzer 11 and the six-way valve 21.
  • the first port of the chemical trap 13 is connected to the second port of the reaction tube 12, and the second port of the chemical trap 13 is connected to the six-way valve 21.
  • Two independently configured branch pipes 28 are provided on the ventilation pipeline 26.
  • a first valve 29 and a second valve 210 are respectively installed on the two branch pipes 28.
  • the first valve 29 is connected to an exhaust device 211 for venting the carrier gas
  • the second valve 210 is connected to a second gas supply device 212 for supplying auxiliary carrier gas.
  • the reaction tube 12 is installed inside the elemental analyzer 11, converting the carbon element in the raw material to be tested into carbon dioxide, and inputting the generated carbon dioxide into the six-way valve 21 through the gas pipeline 26;
  • the first gas supply pipe 16 is used to inject high-speed carrier gas into the device to facilitate the movement of the generated carbon dioxide gas;
  • the chemical trap 13 is used to treat the gas generated by the reaction tube 12, removing moisture from the mixed gas to prevent moisture from affecting the subsequent separation during the low-temperature cryogenic purification process;
  • the first gas supply device 27 provides high-flow-rate carrier gas to the system through the first gas supply pipe 16;
  • the second gas supply device 212 is used to provide auxiliary carrier gas, and the exhaust device 211 can be set to automatically exhaust the gas to realize the automatic exhaust of the system.
  • helium He is chosen as the carrier gas because its liquefaction temperature is much lower than that of carbon dioxide. During cryogenic purification, helium will not liquefy, thus preventing any impact on carbon dioxide.
  • the flow rate of the high-speed carrier gas is 40-100 ml/min.
  • reaction time and temperature of the sample to be processed need to be calibrated using nanomolar-level isotopic standards to determine suitable reaction conditions and ensure that carbon is completely converted into carbon dioxide. If the sample contains two different types of carbon, carbonate carbon and non-carbonate carbon, the optimal reaction temperature and time for each type of carbon can be determined using nanomolar-level isotopic standards to ensure that the two different types of carbon can be converted into carbon dioxide stepwise, thus achieving the purpose of differentiation.
  • the elemental analysis system 1 of this embodiment also includes a vacuum sampler 14 for placing into the sample, the vacuum sampler 14 being connected to a vacuum tube 15 for evacuating a vacuum and a first gas supply tube 16 for introducing high-speed carrier gas.
  • the weighed sample is placed into the vacuum sampler 14, and then the sample in the vacuum sampler 14 is subjected to alternating vacuuming and He gas purging.
  • Each vacuuming and He gas purging process takes 30 seconds, and the process is repeated 5-10 times to remove the interference of carbon in the air on the sample.
  • the ventilation pipe 26 is equipped with two independently configured branch pipes 28.
  • Each branch pipe 28 is equipped with a first valve 29 and a second valve 210.
  • the first valve 29 is connected to a venting device 211
  • the second valve 210 is connected to a second gas supply device 212 for supplying auxiliary carrier gas.
  • the second gas supply device 212 is used to provide the auxiliary carrier gas.
  • auxiliary carrier gas in this embodiment is also helium (He).
  • the second cold trap 25 separates from the second freezing container 24.
  • the vent pipe 26 is connected to the first port of the first cold trap 23 through the six-way valve 21, and the second port of the first cold trap 23 is connected to the vent pipe 218 installed on the six-way valve 21 through the six-way valve 21; when the first cold trap 23 is located inside the first freezing container...
  • the first port of the second cold trap 25 is connected to the third gas supply device 219 via the six-way valve 21, and the second port of the second cold trap 25 is connected to the isotope mass spectrometry analysis system 3.
  • the carbon dioxide mixture after being dehydrated by the chemical trap 13 enters the six-way valve 21, and the six-way valve 21 passes the mixture into the first cold trap 23, which is immersed in the cryogenic freezing liquid, through the first connecting pipe 213.
  • the carbon dioxide in the mixture is frozen by liquid nitrogen.
  • the outlet of the first cold trap 23 is connected to the vent pipe 218 via the second connecting pipe 214 and the six-way valve 21 to ensure the flow of carrier gas.
  • the first cold trap 23 is separated from the first freezing container 22, and the ventilation pipe 26 is connected to the vent pipe 218 after passing through the six-way valve 21; the third gas supply device 219 is connected to the second port of the first cold trap 23 through the six-way valve 21, and the first port of the second cold trap 25 is connected to the first port of the second cold trap 25 through the six-way valve 21.
  • the first cold trap 23 is removed from the cryogenic freezing liquid, and the second cold trap 25 is immersed in the cryogenic freezing liquid.
  • the third gas supply device 219 is connected to the six-way valve 21 through the fourth connecting pipe 216 to provide a low-speed carrier gas.
  • the low-speed carrier gas passes through the six-way valve 21 and then enters the second port of the first cold trap 23 through the third connecting pipe 215.
  • This carries the carbon dioxide that has been re-vaporized in the first cold trap 23 through the first connecting pipe 213 into the six-way valve 21, and then through the fourth connecting pipe 216 into the second cold trap 25, where the mixed gas is again cryogenically frozen and enriched.
  • the carbon dioxide that has been vaporized by the low-speed carrier gas completely enters the second cold trap 25 for cryogenic enrichment.
  • the flow rate of the low-speed carrier gas is 2-10 ml/min.
  • the carbon dioxide in the second cold trap 25 vaporizes and enters the isotope gas mass spectrometry analysis system 3 under a low-flow-rate carrier gas.
  • the isotope mass spectrometry analysis system 3 includes a four-way valve 31 connected to the second port of the second cold trap 25, and the second cold trap 25 is connected to an isotope gas mass spectrometer through the four-way valve 31. 33.
  • the second cold trap 25 is removed from the cryogenic liquid and heated to 150°C to completely release the carbon dioxide.
  • the re-vaporized carbon dioxide under a low-flow-rate carrier gas, passes through the fifth connecting pipe 217 and the four-way valve 31, and then through the four-way valve 31 and the sixth connecting pipe 34 to the interface device 32.
  • the carbon dioxide is then introduced into the isotope gas mass spectrometer 33 through the interface device 32 to facilitate isotope mass spectrometry analysis.
  • the isotope gas mass spectrometer 33 is connected to the second port of the chemical trap 13 via a four-way valve 31.
  • a bypass pipe 4 is provided in this embodiment to connect the chemical trap 13 to the four-way valve 31, and then the mixed gas is introduced into the interface device 32 through the seventh connecting pipe 35, enabling conventional carbon element detection.
  • the weighed sample is placed in the vacuum sampler 14.
  • the sample in the vacuum sampler 14 is subjected to alternating vacuuming and helium purging. Each vacuuming and helium purging process takes 30 seconds. The alternating process is repeated 5-10 times, which can basically remove the interference of carbon in the air on the sample.
  • the processed sample falls into the reaction tube 12 of the elemental analyzer 11, and high-purity oxygen is introduced. At this point, the carrier gas is in high-flow-rate mode (40-100 ml/min for carbon).
  • the reaction time and temperature need to be calibrated using nanomolar-level isotope standards to determine suitable reaction conditions and ensure complete conversion of carbon to carbon dioxide. If the sample contains both carbonate and non-carbonate carbon, nanomolar-level isotope standards can be used to determine the optimal reaction temperature and time for each type of carbon, ensuring that the two types of carbon can be converted to carbon dioxide stepwise for differentiation.
  • the six-way valve 21 While carbon undergoes oxidation and combustion in reaction tube 12, the six-way valve 21 is set as shown in Figure 2, and the first cold trap 23 is lowered into liquid nitrogen to freeze the carbon dioxide generated in the reaction to -196°C. At this time, a high-flow-rate helium carrier gas is used.
  • the six-way valve 21 is set as shown in Figure 3, and simultaneously the second cold trap 25 is lowered into liquid nitrogen for a set time. The carbon dioxide frozen in the first cold trap 23 is completely frozen into the second cold trap 25.
  • helium carrier gas is used at a low flow rate of 2-10 ml/min. After freezing is completed, the second cold trap 25 is lifted and heated to 150°C to ensure that the frozen carbon dioxide is completely released.

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Abstract

本发明属于地球和行星化学仪器设备，公开了一种Nano-C同位素分析装置，包括元素分析系统、二氧化碳冷冻富集系统和同位素质谱分析系统；二氧化碳冷冻富集系统包括六通阀，六通阀连通有第一冷冻组件和第二冷冻组件，第二冷冻组件与同位素质谱分析系统连通；第一冷冻组件包括第一冷冻容器，第一冷冻容器内可升降设置有与六通阀连通的第一冷阱；第二冷冻组件包括第二冷冻容器，第二冷冻容器内可升降设置有与六通阀连通的第二冷阱。本发明机构简单紧凑，使用方便，能针对不同形式存在的碳元素进行分析，进行纳摩尔级别不同形式碳的同位素组成的准确测定，同时能对待检测样本进行多次的富集提纯，降低分析的误差，提高测量的灵敏度和精度。

Description

一种Nano-C同位素分析装置 技术领域
本发明属于地球和行星化学仪器设备技术领域，尤其涉及一种Nano-C同位素分析装置。
背景技术
碳元素不仅是地球上含量丰富的元素之一，同时还是地球上碳基生命的组成和演化的重要元素。板块俯冲作用为地球内部的碳和地表碳的循环提供了驱动力(Dasguptaetal.,2004；Wangetal.,2014；Plank&Manning，2019)，这种碳循环对地球的气候和地表的宜居性会产生巨大的影响(Masonetal.,2017)。利用天然地质样品中的碳同位素不仅可以示踪碳循环过程中的物质来源，还可以示踪碳循环过程中的具体地质作用(Zhengetal.2000；Galvezetal.,2013；Wangetal.,2014；Zhaoetal.,2016；Plank&Manning，2019)。因此，准确测定天然地质样品中的碳同位素组成对于研究地球内部的碳和全球碳循环具有重要科学意义。
天然地质样品中碳的存在形式多种多样，主要分为碳酸盐形式和非碳酸形式；碳酸盐形式包括碳酸根和碳酸氢根与不同阳离子组成的化合物；非碳酸盐形式主要为单质碳(石墨、金刚石等)。利用碳同位素组成的差异，可以有效区分碳的来源，例如可以区分有机碳(如石墨，δ13C平均值--25‰)和无机碳(如海相碳酸盐，δ13C平均值-0‰)。对于不同类型的碳的碳同位素分析的方法主要分为两大类，对于碳酸盐形式的碳同位素分析主要采取酸溶法(McCrea，1950；Brennaetal.,1997；Révész&Landwehr，2002；Paul&Skrzypek，2006)；对于非碳酸盐形式的碳同位素分析主要采取燃烧法(Fuex&Bake，1973；Werneretal.,1999；Zhengetal.,2000；Skrzypek&Paul,2006)。
对于矿物中不同形式碳的各类分析方法的优缺点如下：
McCrea磷酸法是经典的分析方法，属于酸溶的方法，适用于常量的纯碳酸盐分析，该方法属于离线的分析方法(McCrea，1950)；其优点是分析结果的精度较高，适用不同类型的碳酸盐，而不足之处在于，由于是离线的分析方法，需要利用同位素气体质谱仪进行双路进样分析，对于样品量要求较多，一般要求样品量高于10mg；
Gasbench-MS方法也属于酸溶的方法，主要利用Gasbench装置与同位素气体质谱仪联线的在线连续流分析方法(continuousflowmode,Gasbench-CF-IRMS，简写为Gasbench-MS)(Brennaetal.,1997；Révész&Landwehr，2002；Paul&Skrzypek，2006)，适用于小样品量碳酸盐的分析；相较于传统的磷酸法，其优势在于分析结果的精度更高、所需要的样品量更少，可以准确分析微摩尔级别碳的同位素组成(Révész&Landwehr，2002；Paul&Skrzypek，2006；Zhaetal.,2010)；不仅可以分析纯碳酸盐，也可以分析硅酸盐中的微量碳酸盐(Zhaetal.,2010，2018)；但是该方法的不足在于对于碳含量更低的样品，例如纳摩尔级别的碳，无法准确测定；
EA-MS方法属于燃烧氧化的方法，主要是利用元素分析装置combustionElementalAnalyzer与同位素气体质谱仪联线的在线连续流分析方法(Brennaetal.,1997；Werneretal.,1999)；该方法早期主要应用于对有机物样品中碳同位素的分析，也被用于天然地质样品中碳同位素组成的分析(Zhengetal.,2000；Skrzypek&Paul，2006；Zhaetal.,2018)；该方法的优势在于不仅可以分析地质样品中非碳酸盐的碳(例如石墨等)，也可以分析其中碳酸盐的碳(Skrzypek&Paul，2006；Zhaetal.,2018)；可以准确测定微摩尔级别碳的同位素组成(Skrzypek&Paul，2006；Zhaetal.,2018)；但是该方 法的不足在于对于纳摩尔级别的碳，无法准确测定(Zhaetal.,2018)。
当前同位素地球化学和行星化学分析技术的发展，有两个趋势，即“微量”和“微区”。“微量”指的样品中分析对象的含量低于仪器的检测限，因此无法准确测定；“微区”指直接对样品进行原位分析(例如离子探针等)。对于天然样品中不同类型的碳的同位素分析，也存在“微量”的技术瓶颈，例如Zhaetal.(2018)的研究发现，利用Gasbench-MS方法分析硅酸盐中微量碳酸盐的碳同位素组成时，当碳酸盐的量低于30微克，分析结果的准确度和精度都比较差；利用EA-MS方法分析硅酸盐中非碳酸盐碳的同位素组成时，如果样品中碳含量低于500ppm，即使优化称样量，其分析结果仍然非常不理想。
因此，本申请设计了一种Nano-C同位素分析装置来解决上述技术问题。
发明内容
为解决上述技术问题，本发明提出了一种Nano-C同位素分析装置，实现对地球和地外样品中纳摩尔级别不同形式碳的同位素组成的准确测定。
为实现上述目的，本发明提供了一种Nano-C同位素分析装置，包括依次连通的元素分析系统、二氧化碳冷冻富集系统和同位素质谱分析系统；
所述二氧化碳冷冻富集系统包括与所述元素分析系统连通的六通阀，所述六通阀连通有独立设置的第一冷冻组件和第二冷冻组件，所述第二冷冻组件的第二端口与所述同位素质谱分析系统连通；
所述第一冷冻组件包括盛装有冷冻液的第一冷冻容器，所述第一冷冻容器内可升降设置有与所述六通阀连通的第一冷阱；
所述第二冷冻组件包括盛装有冷冻液的第二冷冻容器，所述第二冷冻容器内可升降设置有与所述六通阀连通的第二冷阱。
优选的，所述元素分析系统包括元素分析仪，所述元素分析仪内设置有用 于将待测原材料内的碳元素转换成气态的二氧化碳的反应管，所述反应管的第二端口通过通气管路与所述六通阀的连通，所述通气管路上设置引有供给高速载体气体的第一供气装置。
优选的，所述通气管路上设置有化学阱，所述化学阱设置在所述元素分析仪与六通阀之间，所述化学阱的第一端口与所述反应管的第二端口连通，所述化学阱的第二端口与所述六通阀连通。
优选的，所述通气管路上设置有两个独立设置的分支管，两所述分支管上分别设置有第一阀门和第二阀门，所述第一阀门连通有用于载气排空的排气装置，所述第二阀门连通有用于供给辅助载体气体的第二供气装置。
优选的，当所述第一冷阱位于所述第一冷冻容器内冷冻液面以下对二氧化碳气体进行第一次冷冻时，所述第二冷阱与所述第二冷冻容器分离，所述通气管路通过所述六通阀与所述第一冷阱第一端口连通，所述第一冷阱的第二端口通过所述六通阀与设置在所述六通阀上的排空管连通。
优选的，当所述第一冷阱位于所述第一冷冻容器内对二氧化碳气体进行第一次冷冻时，所述第二冷阱的第一端口与通过所述六通阀连通有第三供气装置，所述第二冷阱的第二端口与所述同位素质谱分析系统连通。
优选的，当所述第二冷阱处于所述第二冷冻容器内冷冻液面以下对二氧化碳气体进行第二次冷冻时，所述第一冷阱与所述第一冷冻容器分离，确保第一冷阱内冷冻富集的二氧化碳可完全冷冻富集于第二冷阱，所述通气管路与通过所述六通阀后与所述排空管连通；所述第三供气装置通过所述六通阀与所述第一冷阱的第二端口连通，所述第二冷阱的第一端口通过所述六通阀与所述第二冷阱的第一端口连通。
优选的，所述第一冷阱与所述第一冷冻容器分离且所述第二冷阱与所述第 二冷冻容器分离时，所述第二冷阱内的冷冻富集的二氧化碳气化后，由所述第三供气装置提供的低速载气进入所述同位素质谱分析系统内。
优选的，所述同位素质谱分析系统包括与所述第二冷阱的第二端口连通的四通阀，所述第二冷阱通过所述四通阀连通有同位素气体质谱仪。
优选的，所述同位素气体质谱仪通过所述四通阀与所述化学阱的第二端口连通，直接连接所述元素分析仪，实现常量分析。
与现有技术相比，本发明具有如下优点和技术效果：本发明功能公开了一种Nano-C同位素分析装置，用于解决极微量碳的同位素分析的技术瓶颈，实现对纳摩尔碳的同位素组成的准确测定；元素分析系统内放入待检测的样本后，再将内部混杂的空气排空，降低空气中的碳元素对检测结果的分析；然后将待检测的样本内的碳元素转换成能进行检测的二氧化碳；生成的二氧化碳就进入二氧化碳冷冻富集系统对二氧化碳进行完全冷冻富集，提高同位素质谱分析系统对二氧化碳进行同位素质谱分析的灵敏度；第一冷冻组件和第二冷冻组件分别工作，实现对产生的气体内的二氧化碳的二次富集纯化，避免二氧化碳逸散导致的分析结果不准确，提高分析下限，实现纳摩尔级别碳同位素分析；二氧化碳第一次冷冻提纯时，第一冷冻组件处于工作状态，第一冷阱浸入第一冷冻容器内的低温冷冻液内，含有二氧化碳的混合气体在第一冷阱内被冷冻，而剩余的载体气体则从六通阀排出；在二氧化碳第二次冷冻富集时，第一冷阱从低温冷冻液内提出，第二冷冻液浸入第二冷冻容器内的低温冷冻液内，第一冷阱内冷冻液化的二氧化碳受热气化后通过六通阀，在低流速载气下进入第二冷阱内，再次进行冷冻富集，提高分析灵敏度；二次冷冻富集主要可利用第二次冷冻后的低流速载气，提高质谱分析的灵敏度，实现对地球和地外样品中纳摩尔级别不同形式碳的同位素组成的准确测定。
本发明机构简单紧凑，使用方便，能针对不同形式存在的碳元素进行分析，实现纳摩尔级别不同形式碳的同位素组成的准确测定。
附图说明
构成本申请的一部分的附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本发明Nano-C同位素分析装置的结构示意图；
图2为本发明二氧化碳冷冻富集系统第一次冷冻分离时的状态示意图；
图3为本发明二氧化碳冷冻富集系统第二次冷冻分离时的状态示意图；
图4为本发明二氧化碳冷冻富集系统二氧化碳排出过程的状态示意图；
图5为本发明Nano-C同位素分析装置的标定和线性图；
图6为本发明Nano-C同位素分析装置的精度分析图；
图中：1、元素分析系统；2、二氧化碳冷冻富集系统；3、同位素质谱分析系统；4、旁通管；11、元素分析仪；12、反应管；13、化学阱；14、真空进样器；15、真空管；16、第一供气管；21、六通阀；22、第一冷冻容器；23、第一冷阱；24、第二冷冻容器；25、第二冷阱；26、通气管路；27、第一供气装置；28、分支管；29、第一阀门；210、第二阀门；211、排空装置；212、第二供气装置；213、第一连接管；214、第二连接管；215、第三连接管；216、第四连接管；217、第五连接管；218、排空管；219、第三供气装置；31、四通阀；32、接口装置；33、同位素气体质谱仪；34、第六连接管；35、第七连接管。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清 楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和具体实施方式对本发明作进一步详细的说明。
参照图1-图6所示，本实施例提供一种Nano-C同位素分析装置，包括依次连通的元素分析系统1、二氧化碳冷冻富集系统2和同位素质谱分析系统3；
二氧化碳冷冻富集系统2包括与元素分析系统1连通的六通阀21，六通阀21连通有独立设置的第一冷冻组件和第二冷冻组件，第二冷冻组件的第二端口与同位素质谱分析系统3连通；
第一冷冻组件包括盛装有冷冻液的第一冷冻容器22，第一冷冻容器22内可升降设置有与六通阀21连通的第一冷阱23；
第二冷冻组件包括盛装有冷冻液的第二冷冻容器24，第二冷冻容器24内可升降设置有与六通阀21连通的第二冷阱25。
本发明功能公开了一种Nano-C同位素分析装置，用于解决极微量碳的同位素分析的技术瓶颈，实现对纳摩尔碳的同位素组成的准确测定；元素分析系统1内放入待检测的样本后，再将内部混杂的空气排空，降低空气中的碳元素对检测结果的分析；然后将待检测的样本内的碳元素转换成能进行检测的二氧化碳；生成的二氧化碳就进入二氧化碳冷冻富集系统2对二氧化碳进行完全冷冻富集，方便通过同位素质谱分析系统3对二氧化碳进行同位素质谱分析；第一冷冻组件和第二冷冻组件分别工作，实现对产生的气体内的二氧化碳的二次冷冻富集，提高分析灵敏度；二氧化碳第一次冷冻提纯时，第一冷冻组件处于工作状态，第一冷阱23浸入第一冷冻容器22内的低温冷冻液内，含有二氧化 碳的混合气体在第一冷阱23内被冷冻液化，而剩余的载体气体则从六通阀21排出；在二氧化碳第二次冷冻提纯时，第一冷阱23从低温冷冻液内提出，第二冷冻液浸入第二冷冻容器24内的低温冷冻液内，第一冷阱23内冷冻液化的二氧化碳受热气化后通过六通阀21在低流速载气下进入第二冷阱25内，再次进行冷冻富集；同时经过二次冷冻提纯还能在此过程中调节载体气体的流速，方便后期低流速载气下的质谱分析，实现对地球和地外样品中纳摩尔级别不同形式碳的同位素组成的准确测定。本发明机构简单紧凑，使用方便，能针对不同形式存在的碳元素进行分析，实现纳摩尔级别不同形式碳的同位素组成的准确测定。
进一步的，低温冷冻液为液氮、干冰等，本实施例的低温冷冻液为液氮，能提供-196℃的低温冷冻温度。
进一步优化方案，通气管路26上设置有化学阱13，化学阱13设置在元素分析仪11与六通阀21之间，化学阱13的第一端口与反应管12的第二端口连通，化学阱13的第二端口与六通阀21连通；通气管路26上设置有两个独立设置的分支管28，两分支管28上分别设置有第一阀门29和第二阀门210，第一阀门29连通有用于载气排空的排气装置211，第二阀门210连通有用于供给辅助载体气体的第二供气装置212。反应管12设置在元素分析仪11内，将待测原材料内的碳元素转换成二氧化碳，并通过通气管路26将生成的二氧化碳输入六通阀21内；第一供气管16用于为装置冲入高速的载体气体，方便带动生成的二氧化碳气体移动；化学阱13的作用是对反应管12产生的气体进行处理，去除混合气体内的水分，防止后续进行低温冷冻提纯过程中的水分对后续的分离产生影响；第一供气装置27通过第一供气管16为系统提供高流速载气；第二供气装置212用于提供辅助载气，排气装置211则能设置自动排气，实现系统的自动排气。
进一步的，本实施例的载体气体选择氦气He，其液化温度远远低于二氧化碳的冷冻温度，在进行冷冻提纯时，氦气不会液化，防止对二氧化碳产生影响。
进一步的，本实施例的高速载体气体的流速为40-100ml/min。
进一步的，待处理的样本反应时间和温度的设定需要利用纳摩尔级别的同位素标准物质进行标定，以确定合适的反应条件，确保其中碳元素完全转化为二氧化碳。如果样品含有碳酸盐碳和非碳酸盐碳两种不同类型的碳，可以利用纳摩尔级别的同位素标准物质分别确定不同类型碳的最佳反应温度和时间，确保两种不同类型碳可以分步转化为二氧化碳，以达到区分的目的。
进一步的，本实施例的元素分析系统1还包括用于放入样本内的真空进样器14，真空进样器14连通有用于抽真空的真空管15和用于通入高速载体气体的第一供气管16。
进一步的，使用时称量好的样品放入真空进样器14中，然后对真空进样器14中的样品进行抽真空和吹扫He气交替处理，每次抽真空和吹扫He气时间均为30秒，交替处理5-10次，去除空气中的碳对样品的干扰。
进一步优化方案，通气管路26上设置有两个独立设置的分支管28，两分支管28上分别设置有第一阀门29和第二阀门210，第一阀门29连通有用于排空装置211，第二阀门210连通有用于供给辅助载体气体的第二供气装置212。第二供气装置212则用于提供辅助载体气体。
进一步的，本实施例的辅助载体气体也是选择氦气He。
进一步优化方案，当第一冷阱23位于第一冷冻容器22内对二氧化碳气体进行第一次冷冻时，第二冷阱25与第二冷冻容器24分离，通气管路26通过六通阀21与第一冷阱23第一端口连通，第一冷阱23的第二端口通过六通阀21与设置在六通阀21上的排空管218连通；当第一冷阱23位于第一冷冻容器 22内对二氧化碳气体进行第一次冷冻时，第二冷阱25的第一端口与通过六通阀21连通有第三供气装置219，第二冷阱25的第二端口与同位素质谱分析系统3连通。经过化学阱13除水后的二氧化碳混合气体进入六通阀21，六通阀21通过第一连接管213将混合气体通入浸泡在低温冷冻液内的第一冷阱23内，混合气体内的二氧化碳被液氮进行冷冻，此时第一冷阱23的出口通过第二连接管214经六通阀21与排空管218连通，确保载气流通。
进一步优化方案，当第二冷阱25处于第二冷冻容器24内对二氧化碳气体进行第二次冷冻时，第一冷阱23与第一冷冻容器22分离，通气管路26与通过六通阀21后与排空管218连通；第三供气装置219通过六通阀21与第一冷阱23的第二端口连通，第二冷阱25的第一端口通过六通阀21与第二冷阱25的第一端口连通。当对二氧化碳进行二次冷冻时，第一冷阱23从低温冷冻液内取出，第二冷阱25浸入低温冷冻液内；同时旋转六通阀21的连通关系，使得通气管路26与排空管218直接排出，而第三供气装置219通过第四连接管216接通六通阀21，提供低速的载体气体，低速载体气体从六通阀21经过后通过第三连接管215通入第一冷阱23的第二端口，带动第一冷阱23内重新气化的二氧化碳通过第一连接管213进入六通阀21，再通过第四连接管216通入第二冷阱25内，再次对混合气体进行低温冷冻富集；低速载体气体的带动气化的二氧化碳完全进入第二冷阱25进行冷冻富集。
进一步的，本实施例的低速载体气体的流速为2-10ml/min。
进一步优化方案，第一冷阱23与第一冷冻容器22分离且第二冷阱25与第二冷冻容器24分离时，第二冷阱25内的二氧化碳气化后在低流速载气下进入同位素质谱分析系统3内；同位素质谱分析系统3包括与第二冷阱25的第二端口连通的四通阀31，第二冷阱25通过四通阀31连通有同位素气体质谱仪 33。当进行质谱分析时，将第二冷阱25从冷冻液中取出，并对第二冷阱25进行150℃的加热，使得二氧化碳完全释放；然后重新气化的二氧化碳在低流速载气下，通过第五连接管217四通阀31，再通过四通阀31经过第六连接管34通入接口装置32，通过接口装置32将二氧化碳通入同位素气体质谱仪33，方便进行同位素质谱分析。
进一步优化方案，同位素气体质谱仪33通过四通阀31与化学阱13的第二端口连通。为了提高本装置的实用性，本实施例设置的旁通管4将化学阱13与四通阀31进行连接，再通过第七连接管35将混合气体通入接口装置32内，可实现常规的碳元素检测。
使用方法：
称量好的样品放入真空进样器14中，对真空进样器14中的样品进行抽真空和吹扫氦气交替处理，每次抽真空和吹扫氦气时间均为30秒，交替处理5-10次，基本可以去除空气中的碳对样品的干扰。
处理好的样品落入元素分析仪11的反应管12中，并通入高纯氧气，此时载气为高流速模式40-100ml/min碳元素，反应时间和温度的设定需要利用纳摩尔级别的同位素标准物质进行标定，以确定合适的反应条件，确保其中碳元素完全转化为二氧化碳。如果样品含有碳酸盐碳和非碳酸盐碳两种不同类型的碳，可以利用纳摩尔级别的同位素标准物质分别确定不同类型碳的最佳反应温度和时间，确保两种不同类型碳可以分步转化为二氧化碳，以达到区分的目的。
在反应管12中碳进行氧化燃烧的同时，将六通阀21设定为图2所示，并将第一冷阱23降入液氮，对反应生成的二氧化碳进行冷冻-196℃，此时为高流速氦气载气。当反应完成，第一冷阱23冷冻完毕后，升起第一冷阱23，六通阀21设为图3所示的状态，同时将第二冷阱25降入液氮，设定足够时间， 将第一冷阱23中冷冻的二氧化碳完全冷冻进第二冷阱25中，此时为低流速2-10ml/min氦气载气，冷冻完成后，抬起第二冷阱25进行加热150℃，确保冷冻的二氧化碳完全释放。
在图4状态下，在低流速2-10ml/min碳元素氦气载气模式下，将第二冷阱25释放的二氧化碳样品气体完全通入同位素气体质谱仪33中，进行碳同位素分析。具体实例：
选取三种碳同位素的国际标准物质，对本发明方法进行验证，三种物质分别为IAEA-CO-1碳酸盐，δ13C＝2.48‰、USGS24石墨，δ13C＝-15.99‰和Merck碳酸盐，δ13C＝-35.58‰。如图5所示，当碳同位素组成在-40‰至+10‰时，分析结果的线性非常好。如图6所示，当碳酸盐的称样量在10纳摩尔-120纳摩尔时，碳同位素分析的精度为±0.11‰-±0.22‰，有着很好的分析精度。因此，本发明解决了碳同位素分析“微量”的技术瓶颈，成功实现了对纳摩尔级别碳同位素的准确测定。
在本发明的描述中，需要理解的是，术语“纵向”、“横向”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。

Claims (10)

  1. 一种Nano-C同位素分析装置，其特征在于：包括依次连通的元素分析系统(1)、二氧化碳冷冻富集系统(2)和同位素质谱分析系统(3)；
    所述二氧化碳冷冻富集系统(2)包括与所述元素分析系统(1)连通的六通阀(21)，所述六通阀(21)连通有独立设置的第一冷冻组件和第二冷冻组件，所述第二冷冻组件的第二端口与所述同位素质谱分析系统(3)连通；
    所述第一冷冻组件包括盛装有冷冻液的第一冷冻容器(22)，所述第一冷冻容器(22)内可升降设置有与所述六通阀(21)连通的第一冷阱(23)；
    所述第二冷冻组件包括盛装有冷冻液的第二冷冻容器(24)，所述第二冷冻容器(24)内可升降设置有与所述六通阀(21)连通的第二冷阱(25)。
  2. 根据权利要求1所述的Nano-C同位素分析装置，其特征在于：所述元素分析系统(1)包括元素分析仪(11)，所述元素分析仪(11)内设置有用于将待测原材料内的碳元素转换成气态的二氧化碳的反应管(12)，所述反应管(12)的第二端口通过通气管路(26)与所述六通阀(21)的连通，所述通气管路(26)上设置引有供给高速载体气体的第一供气装置(27)。
  3. 根据权利要求2所述的Nano-C同位素分析装置，其特征在于：所述通气管路(26)上设置有化学阱(13)，所述化学阱(13)设置在所述元素分析仪(11)与六通阀(21)之间，所述化学阱(13)的第一端口与所述反应管(12)的第二端口连通，所述化学阱(13)的第二端口与所述六通阀(21)连通。
  4. 根据权利要求2所述的Nano-C同位素分析装置，其特征在于：所述通气管路(26)上设置有两个独立设置的分支管(28)，两所述分支管(28)上分别设置有第一阀门(29)和第二阀门(210)，所述第一阀门(29)连通有用于载气排空的排气装置(211)，所述第二阀门(210)连通有用于供给辅助 载体气体的第二供气装置(212)。
  5. 根据权利要求3所述的Nano-C同位素分析装置，其特征在于：当所述第一冷阱(23)位于所述第一冷冻容器(22)内冷冻液面以下对二氧化碳气体进行第一次冷冻时，所述第二冷阱(25)与所述第二冷冻容器(24)分离，所述通气管路(26)通过所述六通阀(21)与所述第一冷阱(23)第一端口连通，所述第一冷阱(23)的第二端口通过所述六通阀(21)与设置在所述六通阀(21)上的排空管(218)连通。
  6. 根据权利要求5所述的Nano-C同位素分析装置，其特征在于：当所述第一冷阱(23)位于所述第一冷冻容器(22)内对二氧化碳气体进行第一次冷冻时，所述第二冷阱(25)的第一端口与通过所述六通阀(21)连通有第三供气装置(219)，所述第二冷阱(25)的第二端口与所述同位素质谱分析系统(3)连通。
  7. 根据权利要求6所述的Nano-C同位素分析装置，其特征在于：当所述第二冷阱(25)处于所述第二冷冻容器(24)内冷冻液面以下对二氧化碳气体进行第二次冷冻时，所述第一冷阱(23)与所述第一冷冻容器(22)分离，确保第一冷阱(23)内冷冻富集的二氧化碳可完全冷冻富集于第二冷阱(25)，所述通气管路(26)与通过所述六通阀(21)后与所述排空管(218)连通；所述第三供气装置(219)通过所述六通阀(21)与所述第一冷阱(23)的第二端口连通，所述第二冷阱(25)的第一端口通过所述六通阀(21)与所述第二冷阱(25)的第一端口连通。
  8. 根据权利要求7所述的Nano-C同位素分析装置，其特征在于：所述第一冷阱(23)与所述第一冷冻容器(22)分离且所述第二冷阱(25)与所述第二冷冻容器(24)分离时，所述第二冷阱(25)内的冷冻富集的二氧化碳气化 后，由所述第三供气装置(219)提供的低速载气进入所述同位素质谱分析系统(3)内。
  9. 根据权利要求8所述的Nano-C同位素分析装置，其特征在于：所述同位素质谱分析系统(3)包括与所述第二冷阱(25)的第二端口连通的四通阀(31)，所述第二冷阱(25)通过所述四通阀(31)连通有同位素气体质谱仪(33)。
  10. 根据权利要求9所述的Nano-C同位素分析装置，其特征在于：所述同位素气体质谱仪(33)通过所述四通阀(31)与所述化学阱(13)的第二端口连通，直接连接所述元素分析仪(11)，实现常量分析。
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