几乎所有小的气相分子(如H2O,CO2等)均具有独特的近红外吸收光谱,在负压条件下,每种微小的气相分子都拥有一对一的特征光谱线,基于这一原理人们开始使用激光光谱(IRIS)技术来准确分析气体样品中的同位素组成。该方法克服了传统同位素比...几乎所有小的气相分子(如H2O,CO2等)均具有独特的近红外吸收光谱,在负压条件下,每种微小的气相分子都拥有一对一的特征光谱线,基于这一原理人们开始使用激光光谱(IRIS)技术来准确分析气体样品中的同位素组成。该方法克服了传统同位素比质谱(isotope ratio mass spectrometry,IRMS)方法的局限性,已经成为公认的高精度、高灵敏度和高准确度的痕量气体检测方法。以大气水汽稳定同位素研究为例,大气水汽稳定同位素组成对水汽源区及其通道上的输送过程等水循环研究有着重要的指示意义。激光光谱技术使得大气水汽氢氧稳定同位素(δ^18O和δD)野外原位连续高分辨率观测成为可能。但是,其观测精度和准确度受仪器运作特点、不同浓度大气水汽对特定光谱吸收性的敏感性差异等因素的影响,通常观测结果具有明显的非线性响应问题。因此,有必要对仪器观测过程中出现的各种偏差进行校正,但现阶段许多用户对新观测技术的国际校正方法尚不清楚。因此,基于波长扫描-光腔衰荡光谱(WS-CRDS)技术的大气水汽同位素观测系统(Picarro L2120-i),通过可调谐二极管激光器(Tunable Diode Laser,TDL)发射可被待测气体分子所吸收的不同波长的激光,测量不同波长下的衰荡时间(即有样品吸收的衰荡时间);TDL发射不能被待测气体吸收的不同波长的激光,测量每个波长下的衰荡时间(相当于无样品吸收的衰荡时间)。通过分析有无样品吸收的衰荡时间差,高精度计算待测气体的分子浓度,进而计算水汽稳定同位素组成。从记忆效应、漂移效应、浓度效应等方面,系统建立了一套准确可靠的大气水汽稳定同位素观测流程与校正方法,为正在使用或将要使用此类设备的研究人员提供参考,以获得高精度和高可靠性的大气水汽稳定同位素观测数据。展开更多
The spatial and temporal distributions of the stable isotopes such as HD16O （or 1H2H16O, or HDO） and H2 18O in atmospheric water vapor are related to evaporation in source places, vapor condensation during transport...The spatial and temporal distributions of the stable isotopes such as HD16O （or 1H2H16O, or HDO） and H2 18O in atmospheric water vapor are related to evaporation in source places, vapor condensation during transport, and vapor convergence and divergence, and thus provide useful information for investigation and understanding of the global water cycle. This paper analyzes spatiotemporal variations of the content of iso- tope HDO （i.e., 5D）, in atmospheric water vapor, namely, δDv, and the relationship of δDv with atmospheric humidity and temperature at different levels in the troposphere, using the HDO and H2O data retrieved from the Tropospheric Emission Spectrometer （TES） at seven pressure levels from 825 to 100 hPa. The results indicate that δDv has a clear zonal distribution in the troposphere and a good correspondence with atmospheric precipitable water. The results also show that δDv decreases logarithmically with atmospheric pressure and presents a decreasing trend from the equator to high latitudes and from lands to oceans. Sea- sonal changes of δDv exhibit regional differences. The spatial distribution and seasonal variation of δDv in the low troposphere are consistent with those in the middle troposphere, but opposite situations occur from the upper troposphere to the lower stratosphere. The correlation between δDv and temperature has a similar distribution pattern to the correlation between δDv and precipitable water in the troposphere. The stable isotope HDO in water vapor （δDv）, compared with that in precipitation （δDp）, is of some differences in spatial distribution and seasonal variation, and in its relationship with temperature and humidity, in- dicating that the impacts of stable isotopic fractionation and atmospheric circulation on the two types of stable isotopes are different.展开更多
文摘几乎所有小的气相分子(如H2O,CO2等)均具有独特的近红外吸收光谱,在负压条件下,每种微小的气相分子都拥有一对一的特征光谱线,基于这一原理人们开始使用激光光谱(IRIS)技术来准确分析气体样品中的同位素组成。该方法克服了传统同位素比质谱(isotope ratio mass spectrometry,IRMS)方法的局限性,已经成为公认的高精度、高灵敏度和高准确度的痕量气体检测方法。以大气水汽稳定同位素研究为例,大气水汽稳定同位素组成对水汽源区及其通道上的输送过程等水循环研究有着重要的指示意义。激光光谱技术使得大气水汽氢氧稳定同位素(δ^18O和δD)野外原位连续高分辨率观测成为可能。但是,其观测精度和准确度受仪器运作特点、不同浓度大气水汽对特定光谱吸收性的敏感性差异等因素的影响,通常观测结果具有明显的非线性响应问题。因此,有必要对仪器观测过程中出现的各种偏差进行校正,但现阶段许多用户对新观测技术的国际校正方法尚不清楚。因此,基于波长扫描-光腔衰荡光谱(WS-CRDS)技术的大气水汽同位素观测系统(Picarro L2120-i),通过可调谐二极管激光器(Tunable Diode Laser,TDL)发射可被待测气体分子所吸收的不同波长的激光,测量不同波长下的衰荡时间(即有样品吸收的衰荡时间);TDL发射不能被待测气体吸收的不同波长的激光,测量每个波长下的衰荡时间(相当于无样品吸收的衰荡时间)。通过分析有无样品吸收的衰荡时间差,高精度计算待测气体的分子浓度,进而计算水汽稳定同位素组成。从记忆效应、漂移效应、浓度效应等方面,系统建立了一套准确可靠的大气水汽稳定同位素观测流程与校正方法,为正在使用或将要使用此类设备的研究人员提供参考,以获得高精度和高可靠性的大气水汽稳定同位素观测数据。
基金Supported by the National Natural Science Foundation of China (40871094 and 41171035)Construction Program of the Key Discipline in Hunan Province (2012001)+1 种基金Open Fund of Key Laboratory of Tibetan Environment Changes and Land Surface Processes of the Chinese Academy of Sciences (2011004)Scientific Research Fund of Hunan Provincial Education Department (09A056)
文摘The spatial and temporal distributions of the stable isotopes such as HD16O （or 1H2H16O, or HDO） and H2 18O in atmospheric water vapor are related to evaporation in source places, vapor condensation during transport, and vapor convergence and divergence, and thus provide useful information for investigation and understanding of the global water cycle. This paper analyzes spatiotemporal variations of the content of iso- tope HDO （i.e., 5D）, in atmospheric water vapor, namely, δDv, and the relationship of δDv with atmospheric humidity and temperature at different levels in the troposphere, using the HDO and H2O data retrieved from the Tropospheric Emission Spectrometer （TES） at seven pressure levels from 825 to 100 hPa. The results indicate that δDv has a clear zonal distribution in the troposphere and a good correspondence with atmospheric precipitable water. The results also show that δDv decreases logarithmically with atmospheric pressure and presents a decreasing trend from the equator to high latitudes and from lands to oceans. Sea- sonal changes of δDv exhibit regional differences. The spatial distribution and seasonal variation of δDv in the low troposphere are consistent with those in the middle troposphere, but opposite situations occur from the upper troposphere to the lower stratosphere. The correlation between δDv and temperature has a similar distribution pattern to the correlation between δDv and precipitable water in the troposphere. The stable isotope HDO in water vapor （δDv）, compared with that in precipitation （δDp）, is of some differences in spatial distribution and seasonal variation, and in its relationship with temperature and humidity, in- dicating that the impacts of stable isotopic fractionation and atmospheric circulation on the two types of stable isotopes are different.
