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用于质谱联用红外激光光谱仪(Picarro)的定量检测方法的开发,以监测氮气基质中H、He、CO、N、Ne、O、Ar、CO₂、H₂S、CH₄、C₂H₄、C₂H₆、C₃H₈、C₄H₁₀、i-C₄H₁₀、n-C₄H₁₀和C₅H₁₂的复杂气体混合物。

Development of quantitative detection method for mass spectrometry coupled to an infrared laser spectroscope (Picarro) to monitor in nitrogen matrix a complex gas mixture of H , He, CO, N , Ne, O , Ar, CO , H S, CH , C H , C H , C H , C H , i-C H , n-C H , and C H.

作者信息

Keita Seny, Noirez Sonia, Berthe Guillaume, Vinsot Agnes, Kim Byeong Seok, Mascle Matthieu, Lundy Mélanie, Garcia Bruno

机构信息

Géosciences, Ressources Naturelles et Environnement (GRNE), Sorbonne Université Faculté des Sciences et Ingénierie, Paris, France.

IFP Energies nouvelles, Rueil-Malmaison, France.

出版信息

Rapid Commun Mass Spectrom. 2023 Oct 15;37(19):e9614. doi: 10.1002/rcm.9614.

DOI:10.1002/rcm.9614
PMID:37698153
Abstract

RATIONALE

The deep geological repository is considered the international reference for radioactive waste management. All gas exchanges must be understood in the context of the feasibility of such a repository. The technological challenge is to continuously monitor a wide range of gaseous molecules at low concentrations in confined spaces.

METHODS

A gas monitoring station, composed of two complementary analyzers, was developed: an electron impact quadrupole mass spectrometer (HPR-20 R&D Hiden Analytical) and an infrared laser spectroscope (Picarro). The spectrometer was calibrated using simple mixtures (i.e., C H in N ) and multiple mixtures (i.e., H , He, CO , CH , and O in N ) at different concentrations to correct interferences. A matrix calculation is proposed to calculate the relative concentrations.

RESULTS

The method developed allows the measurement of gaseous species: light hydrocarbons, noble gases, sulfides, greenhouse gases, oxygen, hydrogen, and nitrogen in the same mixture. For each gas, the SDs and the limits of detection and quantification were calculated. The method was validated by comparing the concentrations of the measured gas species with the reference values of two standard gas cylinders.

CONCLUSIONS

Calibration of a complex gas mixture remains a challenge because fragmentation of molecules, especially hydrocarbons, reduces the sensitivity of the method. The method developed is suitable for continuous gas monitoring in a confined environment and can be implemented to perform experiments in underground structures: galleries, microtunnels (cells), and boreholes.

摘要

原理

深部地质处置库被视为放射性废物管理的国际参考标准。所有气体交换都必须在这样一个处置库的可行性背景下加以理解。技术挑战在于在受限空间内持续监测低浓度的多种气态分子。

方法

开发了一个由两台互补分析仪组成的气体监测站:一台电子轰击四极杆质谱仪(HPR - 20研发型,希登分析仪器公司)和一台红外激光光谱仪(Picarro)。使用简单混合物(即氮气中的甲烷)和不同浓度的多种混合物(即氮气中的氢气、氦气、二氧化碳、甲烷和氧气)对质谱仪进行校准以校正干扰。提出了一种矩阵计算方法来计算相对浓度。

结果

所开发的方法能够测量同一混合物中的气态物质:轻质烃类、稀有气体、硫化物、温室气体、氧气、氢气和氮气。针对每种气体,计算了标准偏差以及检测限和定量限。通过将所测气体物质的浓度与两个标准气瓶的参考值进行比较,对该方法进行了验证。

结论

复杂气体混合物的校准仍然是一项挑战,因为分子的碎片化,尤其是烃类分子的碎片化,会降低该方法的灵敏度。所开发的方法适用于在受限环境中进行连续气体监测,并且可以用于在地下结构中开展实验:巷道、微型隧道(单元)和钻孔。

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