模拟深海环境下热液气体的拉曼光谱实验研究
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摘要
对海底热液物质的探测与研究,是近几十年海洋地质调查研究的重要内容。激光拉曼光谱(Laser Raman Spectrometry)技术能够原位、实时、连续探测海底目标物。我国“十一五”科技攻关计划中作为目标导向类课题“深海原位激光拉曼系统”得到重点立项。本论文立足于该课题的研究,在实验室搭建激光拉曼光谱系统同时利用高温高压实验平台,探测了深海热液区主要气体成分水溶液的拉曼光谱;研究了CO2、CH4、C2H6和C3H8水溶液的拉曼特征峰;得到了各水溶液气体在不同温度及压力下的拉曼特征峰及其变化规律;采用高斯拟合、多项式拟合、线性拟合等多种方法处理低信噪比的复杂拉曼光谱数据,为深海环境下应用激光拉曼技术反演物质成分及环境信息提供参考。
本文在实验室中搭建由激发波长532nm的Nd:YAG激光器,单光栅光谱仪和CCD组成的激光拉曼光谱系统,利用高温高压平台模拟深海热液口环境(最高压力40MPa,最高温度350℃),对深海热液区的主要成分CO2、CH4、C2H6和C3H8及部分混合物的水溶液在不同压力和温度条件下的拉曼光谱进行探测和分析,结果显示:常温40MPa压力下CO2水溶液的Fermi双峰分别位于1384.9cm-1和1278.3cm-1处,CH4的水溶液拉曼峰ν1位于2912.1cm-1处,C2H6有三个拉曼特征峰,分别对应于ν3(C-C伸缩振动)997.4cm-1,ν1(CH3对称伸缩振动)2893.7cm-1和2ν11(CH3扭曲伸缩振动)2950.4cm-1;而C3H8结构最复杂拉曼峰也最多,本文得到C3H8的四个拉曼特征峰,分别位于908.6cm-1(C-C伸缩振动),2835.5、2882.8和2960.8cm-1(C-H伸缩振动),均比其气相的拉曼频移低3~8cm-1;常温下,由于水分子的影响各自水溶液的拉曼特征峰随压力(≤40MPa)的变化均无明显移动;在40MPa的压力下随着温度的升高(≤350℃),CO2水溶液的Fermi双峰分别向高波数区移动了约3.4cm-1和7.0cm-1,而CH4水溶液的拉曼峰ν1向低波数区移动了约3.1cm-1,C2H6和C3H8水溶液的拉曼特征峰也均向低波数区有不同程度的移动;在CO2和CH4混合水溶液升温过程中CO2的双峰分别向高波数区移动了约4.3cm-1和3.8cm-1,CH4的特征峰ν1向低波数区移动了4.5cm-1。对其进行线性拟合,相关系数R>0.83说明在室温到350℃范围内温度的变化对其水溶液拉曼频移有影响,频移量与温度线性相关。
The measurement and study of underwater hydrothermal materials has been an important topic of marine geological research for the recent decades. The technology of Laser Raman Spectrometry can measure underwater target in situ, in real time and continuously. Deep-sea in-situ laser Raman system, one of the guide- line subjects in China's“Eleventh Five-Year Plan”for scientific research, has been established as a key project. The work of this thesis is carried out under this key project. We constructed a Laser Raman Spectrometry system in our laboratory, and utilized a high-temperature, high-pressure experimental platform to carry out the following studies: Raman spectra measurement of the aqueous solution of the main gas compositions in deep-sea hydrothermal areas; study of Raman peaks of CO2, CH4, C2H6 and C3H8 in aqueous solutions; recording these Raman peaks and their changes under different temperature and pressure; processing of complex Raman spectra with low signal-to-noise ratio with various methods including Gaussian fitting, polynomial fitting and linear regression. These studies provide data and reference for using laser Raman technology to extrapolate material composition and environmental information in deep-sea environment.
In this thesis, we built a Nd: YAG laser with an emission wavelength of 532nm, a single-grating spectrometer and a laser Raman spectroscopy system with CCD. We used a high-temperature high-pressure platform to simulation the environment of a deep-sea hydrothermal vent (with maximum pressure of 40MPa and maximum temperature of 350℃). Under different pressure and temperature, we measured and analyzed the Raman spectra of the key compositions of deep-sea hydrothermal area, i.e. the aqueous solutions of CO2, CH4, C2H6, C3H8 and some of their admixture. The results show that at room temperature and 40MPa, the CO2 solution exhibits Fermi double peaks at 1384.9cm-1and 1278.3cm-1; the CH4 solution shows the Raman peakν1 at 2912.1cm-1; the C2H6 shows three Raman peaks that correspond toν3 (C-C stretch) at 997.4cm-1,ν1 (CH3 sym stretch) at 2893.7cm-1, and 2ν11 (CH3 d-stretch) at 2950.4cm-1, respectively; C3H8 has the most complicated structure and therefore the most Raman peaks. We obtained four peaks for that are located at 908.6cm-1 (C-C stretch), 2835.5, 2882.8 and 2960.8cm-1 (C-H stretch). All the peaks are shifted by 3~8cm-1 compared to the corresponding Raman peaks in gaseous phase. At room temperature no Raman peak of the aqueous solutions exhibit significant shift with changing pressure (≤40MPa), due to the presence of water molecules. At 40MPa and with increasing temperature (≤350℃), the Fermi peaks of CO2 solution shift toward higher wave number by 3.4cm-1 and 7.0cm-1, respectively; theν1 peak of CH4 solution is shifted to lower wave number by 3.1cm-1, Raman peaks of C2H6 solution and C3H8 solution are all shifted to lower wave number with varying magnitude; in the aqueous solution of CO2 and CH4 mixture, the CO2 Fermi double peaks are shifted higher by 4.3cm-1 and 3.8cm-1 respectively during the increase of temperature, while the CH4ν1 peak is shifted lower by 4.5cm-1. After a linear regression of these data, a correlation coefficient of R > 0.83 is obtained, which shows that from room temperature to 350℃, temperature changes affects the Raman frequency shift, the amount of which is linearly correlated with temperature.
本文在实验室中搭建由激发波长532nm的Nd:YAG激光器,单光栅光谱仪和CCD组成的激光拉曼光谱系统,利用高温高压平台模拟深海热液口环境(最高压力40MPa,最高温度350℃),对深海热液区的主要成分CO2、CH4、C2H6和C3H8及部分混合物的水溶液在不同压力和温度条件下的拉曼光谱进行探测和分析,结果显示:常温40MPa压力下CO2水溶液的Fermi双峰分别位于1384.9cm-1和1278.3cm-1处,CH4的水溶液拉曼峰ν1位于2912.1cm-1处,C2H6有三个拉曼特征峰,分别对应于ν3(C-C伸缩振动)997.4cm-1,ν1(CH3对称伸缩振动)2893.7cm-1和2ν11(CH3扭曲伸缩振动)2950.4cm-1;而C3H8结构最复杂拉曼峰也最多,本文得到C3H8的四个拉曼特征峰,分别位于908.6cm-1(C-C伸缩振动),2835.5、2882.8和2960.8cm-1(C-H伸缩振动),均比其气相的拉曼频移低3~8cm-1;常温下,由于水分子的影响各自水溶液的拉曼特征峰随压力(≤40MPa)的变化均无明显移动;在40MPa的压力下随着温度的升高(≤350℃),CO2水溶液的Fermi双峰分别向高波数区移动了约3.4cm-1和7.0cm-1,而CH4水溶液的拉曼峰ν1向低波数区移动了约3.1cm-1,C2H6和C3H8水溶液的拉曼特征峰也均向低波数区有不同程度的移动;在CO2和CH4混合水溶液升温过程中CO2的双峰分别向高波数区移动了约4.3cm-1和3.8cm-1,CH4的特征峰ν1向低波数区移动了4.5cm-1。对其进行线性拟合,相关系数R>0.83说明在室温到350℃范围内温度的变化对其水溶液拉曼频移有影响,频移量与温度线性相关。
The measurement and study of underwater hydrothermal materials has been an important topic of marine geological research for the recent decades. The technology of Laser Raman Spectrometry can measure underwater target in situ, in real time and continuously. Deep-sea in-situ laser Raman system, one of the guide- line subjects in China's“Eleventh Five-Year Plan”for scientific research, has been established as a key project. The work of this thesis is carried out under this key project. We constructed a Laser Raman Spectrometry system in our laboratory, and utilized a high-temperature, high-pressure experimental platform to carry out the following studies: Raman spectra measurement of the aqueous solution of the main gas compositions in deep-sea hydrothermal areas; study of Raman peaks of CO2, CH4, C2H6 and C3H8 in aqueous solutions; recording these Raman peaks and their changes under different temperature and pressure; processing of complex Raman spectra with low signal-to-noise ratio with various methods including Gaussian fitting, polynomial fitting and linear regression. These studies provide data and reference for using laser Raman technology to extrapolate material composition and environmental information in deep-sea environment.
In this thesis, we built a Nd: YAG laser with an emission wavelength of 532nm, a single-grating spectrometer and a laser Raman spectroscopy system with CCD. We used a high-temperature high-pressure platform to simulation the environment of a deep-sea hydrothermal vent (with maximum pressure of 40MPa and maximum temperature of 350℃). Under different pressure and temperature, we measured and analyzed the Raman spectra of the key compositions of deep-sea hydrothermal area, i.e. the aqueous solutions of CO2, CH4, C2H6, C3H8 and some of their admixture. The results show that at room temperature and 40MPa, the CO2 solution exhibits Fermi double peaks at 1384.9cm-1and 1278.3cm-1; the CH4 solution shows the Raman peakν1 at 2912.1cm-1; the C2H6 shows three Raman peaks that correspond toν3 (C-C stretch) at 997.4cm-1,ν1 (CH3 sym stretch) at 2893.7cm-1, and 2ν11 (CH3 d-stretch) at 2950.4cm-1, respectively; C3H8 has the most complicated structure and therefore the most Raman peaks. We obtained four peaks for that are located at 908.6cm-1 (C-C stretch), 2835.5, 2882.8 and 2960.8cm-1 (C-H stretch). All the peaks are shifted by 3~8cm-1 compared to the corresponding Raman peaks in gaseous phase. At room temperature no Raman peak of the aqueous solutions exhibit significant shift with changing pressure (≤40MPa), due to the presence of water molecules. At 40MPa and with increasing temperature (≤350℃), the Fermi peaks of CO2 solution shift toward higher wave number by 3.4cm-1 and 7.0cm-1, respectively; theν1 peak of CH4 solution is shifted to lower wave number by 3.1cm-1, Raman peaks of C2H6 solution and C3H8 solution are all shifted to lower wave number with varying magnitude; in the aqueous solution of CO2 and CH4 mixture, the CO2 Fermi double peaks are shifted higher by 4.3cm-1 and 3.8cm-1 respectively during the increase of temperature, while the CH4ν1 peak is shifted lower by 4.5cm-1. After a linear regression of these data, a correlation coefficient of R > 0.83 is obtained, which shows that from room temperature to 350℃, temperature changes affects the Raman frequency shift, the amount of which is linearly correlated with temperature.
引文
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