Comparison of Raman spectral characteristics and quantitative methods between 13CH4 and 12CH4 from 25 to 400 °C and 50 to 400 bar

doi:10.1016/j.saa.2023.123380

	Comparison of Raman spectral characteristics and quantitative methods between 13CH4 and 12CH4 from 25 to 400 °C and 50 to 400 bar
	Ge, Yuzhou 1,2,3,4; Li, Lianfu1,2,4 ; Xi, Shichuan1,2,4 ; Zhang, Yitong 1,2,3,4; Luan, Zhendong 1,2,3,4; Zhang, Xin 1,2,3,4
	2024-01-05
发表期刊	SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
ISSN	1386-1425
卷号	304 页码:13
通讯作者	Zhang, Xin([email protected])
摘要	In recent years, increasing attention has been given to quantifying the isotopic compositions of gases by Raman spectroscopy. However, related research on the carbon isotopes of CH4 is still lacking. In this study, the Raman spectral characteristics of 13CH4 and 12CH4 in the pure CH4 system and in the CH4-H2O system are comprehensively studied at temperatures ranging from 25 to 400 degrees C and pressures ranging from 50 to 400 bar. For the pure CH4 system, the peak positions of the symmetric stretching band (v1) of 13CH4 and 12CH4 both shift to a higher wavenumber with increasing temperature and decreasing pressure, and their full width at half maximum (FWHM) values can reach 4.7 cm- 1 and 5.5 cm- 1, respectively, with increasing temperature and density. The peak position of the v1 band of 13CH4 is always 4.6-5.1 cm- 1 lower than that of 12CH4 under the same conditions, indicating that 13CH4 and 12CH4 can be distinguished by peak position and FWHM in the Raman spectra. Although the calculated Raman shifts (v0) at zero-density for 13CH4 and 12CH4 are different, the unified equation for determining the density of CH4-rich fluid inclusions is still applicable, as long as to bracket the sample measurement with measurements of reference standards. For the CH4-H2O system, the peak position of the v1 band of dissolved 13CH4 is approximately 2.5 cm- 1 lower than that of 12CH4, while their FWHM values can be more than 12.2 cm-1, causing more difficulty in distinguishing them in aqueous solutions. In addition, Raman quantitative calibration models of 12CH4 and 13CH4 in the CH4-H2O system are established. The difference in the Raman scattering cross section (RSCS) of dissolved 12CH4 and 13CH4, rather than changes in the molar density or RSCS of water is the main reason leading to the difference in the Raman quantitative calibration models of CH4 concentrations between the 12CH4-H2O system and the 13CH4-H2O system. Our work provides a good reference for the in situ identification and quantification of the carbon isotopic composition of CH4 in high-temperature and high-pressure environments.
关键词	Raman spectroscopy In situ Quantitative analysis Carbon isotope 13 CH 4 12 CH 4
DOI	10.1016/j.saa.2023.123380
收录类别	SCI
语种	英语
资助项目	National Natural Science Foundation of China[92058206]; National Natural Science Foundation of China[42106184]; National Natural Science Foundation of China[42221005]; National Natural Science Foundation of China[41822604]; Strategic Priority Research Program, CAS[XDA22050102]; Strategic Priority Research Program, CAS[XDA19060402]; Open Fund of the Key Laboratory of Marine Geology and Environment, CAS[MGE2021KG06]; Young Taishan Scholars Program[tsqn201909158]; China Postdoctoral Science Foundation[2020M682245]; Natural Science Foundation of Shandong Province[ZR2021QD046]; Special Research Assistant Project of Chinese Academy of Sciences
WOS研究方向	Spectroscopy
WOS类目	Spectroscopy
WOS记录号	WOS:001300778600001
出版者	PERGAMON-ELSEVIER SCIENCE LTD
WOS关键词	CARBON-ISOTOPE FRACTIONATION ; UPPER-MANTLE TEMPERATURES ; METHANE-BEARING MELT ; O-H-N ; FLUID INCLUSIONS ; HIGH-PRESSURE ; HYDROTHERMAL VENT ; CH4 ; WATER ; SOLUBILITY
引用统计	被引频次：3[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.qdio.ac.cn/handle/337002/198165
专题	深海极端环境与生命过程研究中心
通讯作者	Zhang, Xin
作者单位	1.Chinese Acad Sci, Ctr Ocean Mega Sci, CAS Key Lab Marine Geol & Environm, Qingdao 266071, Peoples R China 2.Chinese Acad Sci, Inst Oceanol, Ctr Deep Sea Res, Ctr Ocean Mega Sci, Qingdao 266071, Peoples R China 3.LaoShan Lab, Lab Marine Geol, Qingdao 266061, Peoples R China 4.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Ge, Yuzhou,Li, Lianfu,Xi, Shichuan,et al. Comparison of Raman spectral characteristics and quantitative methods between 13CH4 and 12CH4 from 25 to 400 °C and 50 to 400 bar[J]. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY,2024,304:13.
APA	Ge, Yuzhou,Li, Lianfu,Xi, Shichuan,Zhang, Yitong,Luan, Zhendong,&Zhang, Xin.(2024).Comparison of Raman spectral characteristics and quantitative methods between 13CH4 and 12CH4 from 25 to 400 °C and 50 to 400 bar.SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY,304,13.
MLA	Ge, Yuzhou,et al."Comparison of Raman spectral characteristics and quantitative methods between 13CH4 and 12CH4 from 25 to 400 °C and 50 to 400 bar".SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY 304(2024):13.