基于傅里叶变换红外光谱法CO2气体碳同位素比检测研究

介绍了基于傅里叶变换红外技术检测CO₂气体碳同位素比的新方法, 详细介绍了如何从HITRAN红外数据库中提取气体标准吸收截面; 介绍了基于非线性最小二乘法反演CO₂气体碳同位素比和整套实验装置的组成及实验步骤. 从理论和实验分析两方面讨论了温度和气压变化对δ¹³CO₂值的影响规律. 对于同一CO₂标准气体, 采用FTIR和同位素质谱法两种技术进行了δ¹³CO₂值对比检测, 两种测量技术的平均值差异仅为0.25%. 从实验结果可以看出, FTIR技术可以实现对CO₂气体碳同位素比的检测.     

傅里叶变换红外光谱法测量大气中CO2和H2O的稳定同位素

光谱技术的发展使得连续测量环境大气中的稳定同位素成为可能。描述了应用傅里叶变换红外(FTIR)光谱技术测量环境大气中稳定同位素的方法。为了验证该方法对环境大气中的稳定同位素进行连续测量的可行性,在七天的外场实验中,应用开放光程FTIR系统直接测量环境大气中CO2的稳定同位素12 CO2,13 CO2和H2O的稳定同位素H216 O和HD16 O,并得到大气中碳同位素比值δ13 C和氘同位素比值δD。对同位素比值δ13 C和δD,系统的测量精度分别约为1.08‰和1.32‰。采用Keeling图方法,在不同的时间尺度上对CO2和H2O的同位素数据进行分析,得到了水汽地表蒸散的氘同位素特征δET。外场实验的结果证明了开放光程FTIR系统长期测量环境大气中稳定同位素的潜力。     

基于傅里叶变换红外光谱技术测量大气中CO_2的稳定同位素比值

长期监测大气中CO_2及其稳定同位素不仅可以获得CO_2源和汇信息,还可以确定不同排放源对大气中CO_2的贡献.傅里叶变换红外光谱技术是目前大气中痕量气体柱浓度高精度遥测的一种重要方法.本研究基于地基高分辨率傅里叶变换红外光谱仪采集的近红外太阳吸收光谱反演出大气中CO_2的稳定同位素~(13)CO_2和~(12)CO_2.在选择的~(13)CO_2的三个光谱窗口和~(12)CO_2的两个光谱窗口光谱拟合残差都很小,光谱拟合质量高.实验观测期间CO_2同位素~(13)CO_2和~(12)CO_2的反演误差平均值分别为(1.18±0.27)%和(0.89±0.25)%;利用Allan方差计算出观测系统的碳同位素比值δ~(13)C的测量精度为0.041‰.获得了2015年9月18日至2016年9月24日一年内大气中碳同位素比值δ~(13)C的长时间序列.结果表明,在整个测量期间δ~(13)C在-7.58‰--11.66‰范围内变化,平均值为(-9.5±0.57)‰;δ~(13)C有着明显的季节变化,冬季最小,夏季最大.分析了取暖导致的化石燃料燃烧排放增多是冬季大气中CO_2重同位素~(13)CO_2贫化的原因.观测结果显示了高分辨率傅里叶变换红外光谱仪具有准确和高精度观测大气中CO_2的稳定同位素和同位素比值δ~(13)C的能力.     

利用便携式FTIR光谱仪研究环境大气中CO2浓度变化

高准确和高精度测量环境大气CO₂浓度,对于监测区域和城市温室气体的排放至关重要。基于傅里叶变换红外（FTIR）光谱技术,利用便携式FTIR光谱仪采集近红外太阳吸收光谱,基于非线性最小二乘算法,反演获得了2016年9月至2020年5月期间合肥地区环境大气的CO₂柱浓度。观测结果表明,CO₂气体的柱浓度有着明显的季节变化,在春季出现最大值,夏季下降速度快,秋季达到最小值。柱平均干空气混合比浓度XCO₂的日均值位于(401.23±0.60)和(418.41±0.31) ppm之间,而2017年观测的月均值有着6.96 ppm的季节幅值。并且,观测期间XCO₂呈现逐年增长的趋势,年平均增长率为(2.71±0.66) ppm·yr-1。为了验证便携式FTIR光谱仪观测的准确性和可靠性,我们将其观测结果与高分辨率FTIR仪器同步测量结果进行比较,发现观测的XCO₂的偏差均值为1.32 ppm,二者的相关系数r为0.97,两个数据显示高度一致性。同时将观测结果与GOSAT卫星数据作了横向比较,两个数据的平均偏差为(0.63±1.76) ppm,二者的相关系数r为0.86,显示出地基数据与卫星数据有高相关性。最后,将合肥站点2020年秋季观测数据与上海站点同期观测数据进行了比较,发现上海站点与合肥站点的CO₂柱浓度变化基本一致,合肥观测点的XCO₂日均值位于(415.09±0.84)和(417.80±0.67) ppm之间,上海观测点的XCO₂日均值位于(411.87±1.07)和(416.63±1.70) ppm之间,表明同步观测期间合肥的CO₂柱浓度略高于上海市。地基FTIR光谱仪的观测结果可为追踪合肥地区温室气体的碳源与碳汇提供基础数据。     

应用于高精度大气CO_2遥感的空间外差技术研究

针对大气二氧化碳高精度反演对卫星载荷测量技术的极高要求,通过与传统的色散型和干涉型光谱测量技术的比较,介绍了一种新型的超光谱测量技术即空间外差光谱技术。依据航天条件下的载荷技术需求,较详细地介绍了探测原理和仪器结构,展示了这种技术获取超光谱分辨率和高信噪比数据的能力,以及小体积、轻质量和低功率等在航天环境下的重要技术优势。在此基础上,利用本所自主研制的原理样机进行了大气二氧化碳探测实验,结果表明其观测数据精度能够良好地应用于二氧化碳反演,其探测结果与日本碳嗅卫星(GOSAT)观测结果相一致,说明空间外差技术具有应用于卫星对地探测大气二氧化碳的能力。     

利用傅里叶变换红外光谱技术连续测量环境大气中水汽的稳定同位素

傅里叶变换红外(FTIR)光谱技术可用来测量宽带红外光谱,能同时分析大气中的多种成分。描述了利用开放光路FTIR光谱技术测量环境大气中水汽的稳定同位素的新方法。以分析采集的中红外光谱为基础,在外场实验中,应用开放光程FTIR系统连续测量环境大气中水汽的稳定同位素H216 O和HD16 O,并得到大气中的氘同位素比值δD。对该测量系统,H216 O和HD16 O的测量误差分别约为0.25%和1.60%,氘同位素比值δD的测量精度约为1.32‰。详细分析了其中5天的数据,研究了环境大气中水汽的稳定同位素H216 O、HD16 O以及同位素比值δD随时间的变化规律。并采用Keeling图分析方法,研究了地表蒸散的氘同位素特征。外场实验的结果证明了所提的测量方法和开放光程FTIR系统相结合长期测量环境大气中稳定同位素的能力。     

(NH4)2SO4，NH4NO3和(NH4)2SO4/NH4NO3混合气溶胶吸湿质量增长因子的快速测量方法

气溶胶颗粒的吸湿性决定了其尺寸、浓度、化学组成以及相态,从而显著影响着全球气候、大气异相化学以及人类健康。运用在线、原位、连续扫描衰减全反射傅里叶变换红外光谱（ATR-FTIR）技术, 结合线性湿度（RH）控制系统,实现了RH连续变化条件下气溶胶FTIR-ATR光谱的快速测量。根据水弯曲振动谱带（~1 640 cm-1）峰面积随RH的变化,得到了(NH₄)₂SO₄,NH₄NO₃和(NH₄)₂SO₄/NH₄NO₃混合气溶胶的质量增长因子（MGFs）、潮解点（DRH）和风化点（ERH）。与气溶胶的E-AIM模型预测值相比较,实验结果表现出良好的一致性,证实该方法是一种测量大气气溶胶MGFs,ERH和DRH的快速测量方法。     

双重傅里叶变换红外椭偏光谱系统的研制

介绍一种新型红外椭圆偏振光谱实验系统。实验中采用了对光子能量和方位角作双傅里叶变换,及同步旋转检偏和超偏器（RAP）的方法,根据傅里叶变换的四个余弦交流分量,计算相应的光学常数。经过对实验系统各误差来源的分析和纠正,提高了实验精度,使误差控制在1％以内。测量了Au等样品的红外介电函数谱,并用德鲁得（Drude)模型作拟俣运算,获得了与理论计算相一致的结果。     

FTIR被动遥测信噪比优化及在变电站SF6泄漏检测应用

被动FTIR红外遥测技术可应用于气体泄漏检测,气体检测下限与仪器信噪比密切相关。仪器信噪比与测量参数有关,如光谱分辨率、采样频率、积分时间、平均次数等,如何结合实际应用优化参数组合以实现最佳信噪比,目前还缺少系统分析。针对这一问题,从理论上分析了这些参数与信噪比关系,并归类为三个方面：（1）光谱分辨率,引用了Roland Harig给出的结论,当光谱分辨率低于特征峰半高全宽时,信噪比不变,但为了避免背景气体的交叉干扰,分辨率不宜设置过低,需要结合实际应用综合考虑;（2）降低采样频率能够减少计算量,缩小光谱范围,但采样频率和光谱范围与信噪比无关;（3）在积分时间和光谱平均次数方面,同样时间条件下,多次干涉图采集会引入零光程差的采样误差,使得噪声大于理论计算值,因而长积分时间获得信噪比优于多次平均。开展了六氟化硫（SF₆）泄漏检测实验,根据SF₆特征峰宽度选择4 cm-1分辨率,20 kHz采样频率兼顾了信噪比和检测时间,并利用FTIR巡检系统发现变电站泄漏点,证明了方法的有效性。     

大气气溶胶中NO3ˉ的光学特性研究

利用傅里叶变换红外光谱技术分析比较了大气气溶胶和NH4NO3的红外光谱,结果显示大气气溶胶和NH4NO3中的NO3-的红外光谱特征基本保持一致。通过NH4NO3中NO3-的透过率的大小计算出了NO3-的吸收系数α和质量吸收截面κ,利用所得吸收系数进一步求出了其复折射率的虚部,经过K-K(Kramers-Kroning)关系的转换,求得其复折射率的实部,实验结果对分析大气气溶胶中各化学组分的散射和吸收效应有着极其重要的意义。     

Air pressure broadening and shifting of high-J lines of (00011) ← (00001) band of CO2

The absorption spectra of carbon dioxide (isotope 626, natural abundance in air, ambient temperature) have been studied at total pressures 68-570 Torr with spectral resolution 0.003-0.005 cm⁻¹. The spectra were measured in the spectral domain of 2273-2393 cm⁻¹ by FTIR spectrometer Bruker IFS 125 HR equipped with White-type multipass cell (6.4-41.6 m) and with a cell having 10 cm optical path length. Pressure broadening and shift coefficients were obtained from a series of spectra by means of a nonlinear least-squares spectral fitting technique for the lines of the (00011)←(00001) band with rotational quantum number up to J=82. For fitting of the individual line shapes, we used the Voigt profile with pre-calculated Doppler broadening parameter. The experimental pressure broadening and shift coefficients are compared with the values available in spectroscopic databases HITRAN 2008 and Carbon Dioxide Spectroscopic Databank (CDSD-296) and with other experimental values reported in the literature.     

Fourier transform spectroscopy of CO2 and OCO in the 3800-8500 cm region and the global modeling of the absorption spectrum of CO2

The absorption spectrum of the ¹⁸O enriched carbon dioxide has been recorded at Doppler limited resolution with a Fourier transform spectrometer in the spectral range 3800-8500 cm⁻¹. Seventeen cold bands (14Σ-Σ and 3Σ-Π) and nine hot bands (9Π-Π) of ¹²C¹⁸O₂, nineteen cold bands (18Σ-Σ and 1Σ-Π) and eighteen hot bands (6Σ-Σ, 9Π-Π and 3Δ-Δ) of ¹⁶O¹²C¹⁸O have been observed. Among them, 14 ¹²C¹⁸O₂ bands and 12 ¹⁶O¹²C¹⁸O bands are observed for the first time. The spectroscopic parameters G_v, B_v, and centrifugal distortion constants, have been determined for all observed bands. Effective Hamiltonian parameters for the ¹²C¹⁸O₂ isotopic species are retrieved from the global fitting of the observed line positions presented in this paper and collected from the literature. As the result, 65 obtained effective Hamiltonian parameters reproduce 5443 observed line positions of 73 ¹²C¹⁸O₂ bands with RMS = 0.00145 cm⁻¹.     

CO2: Global Treatment of Vibrational–Rotational Spectra and First Observation of the 2ν1 + 5ν3 and ν1 + 2ν2 + 5ν3 Absorption Bands

The effective operator approach is applied to the calculation of both line positions and line intensities of the ¹³C¹⁶O₂ molecule. About 11 000 observed line positions of ¹³C¹⁶O₂ selected from the literature have been used to derive 84 parameters of a reduced effective Hamiltonian globally describing all known vibrational–rotational energy levels in the ground electronic state. The standard deviation of the fit is 0.0015 cm⁻¹. The eigenfunctions of this effective Hamiltonian have then been used in fittings of parameters of an effective dipole-moment operator to more than 600 observed line intensities of the cold and hot bands covering the ν₂ and 3ν₂ regions. The standard deviations of the fits are 3.2 and 12.0% for these regions, respectively. The quality of the fittings and the extrapolation properties of the fitted parameters are discussed. A comparison of calculated line parameters with those provided by the HITRAN database is given. Finally, the first observations of the 2ν₁ + 5ν₃ and ν₁ + 2ν₂ + 5ν₃ absorption bands by means of photoacoustic spectroscopy (PAS) is presented. The deviations of predicted line positions from observed ones is found to be less than 0.1 cm⁻¹, and most of them lie within the experimental accuracy (0.007 cm⁻¹) once the observed line positions are included in the global fit.     

Absolute line intensities of CO2 in the 3090-3920 cm region

Absolute line intensities of ¹³C¹⁶O₂ were retrieved from high-resolution Fourier transform spectra recorded in the region 3090-3920 cm⁻¹. The uncertainty of the line intensity determination is estimated to be between 3 and 5% for the strong lines. The global fittings of the observed line intensities within the framework of the effective operators approach have been performed, reaching the experimental accuracy. A comparison of newly measured line intensities with those found in the HITRAN database is presented.     

Absolute line intensities of CO2 in the 4200-8500 cm region

The absolute line intensities of ¹³C¹⁶O₂ were retrieved from Fourier-transform spectra recorded in the region 4200-8500 cm⁻¹. The accuracy of the line intensity determination is estimated to be 5% or better for most lines and about 10% for weak ones. The vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined. The global fittings of the observed line intensities within the framework of the effective operators approach have been performed. As the result of the fittings, most line intensities are reproduced within the experimental accuracy. The comparison between the new measured data and the HITRAN database are also carried out.     

CO2/CO2 isotopic ratio measurements with a continuous-wave quantum cascade laser in exhaled breath

A laser spectrometer based on a continuous-wave thermoelectrically-cooled distributed feedback quantum cascade laser at ∼2308 cm⁻¹ has been evaluated for measurement of ¹³CO₂/¹²CO₂ isotopic ratio (δ¹³C) changes in exhaled breath samples and in CO₂ gas flows in the concentration range 1-5%. Mid-infrared CO₂ absorption spectra were measured in a 54.2-cm long optical cell using balanced detection whereby the beam passing through the cell was ratioed against a reference beam split-off from the main beam before the cell. Signal-to-noise ratios (SNR) were estimated for CO₂ concentration measurements determined from either absorption peak amplitude or absorption peak area. The highest SNR were achieved in the measurements based upon a fitted absorption peak area. Typical short-term δ¹³C precisions of 1.1⁰/₀₀ (1-s integration time) and 0.5⁰/₀₀ (8-12-s integration time) were estimated from the two-sample (Allan) variance plots of data recorded in the optical cell at a pressure of 20 Torr and with no active temperature stabilization of the cell and gas flow. The best precision of 0.12⁰/₀₀ was achieved for averaging 80 successive 1-s integration time measurements.     

Computations of temperature dependences for line shape parameters in the 30012 ← 00001 and 30013 ← 00001 bands of pure CO2

In this study, we have calculated the broadening and first order line mixing parameters for over 100 transitions in the 30012 ← 00001 and 30013 ← 00001 bands of carbon dioxide. The calculations were performed over the 193–323 K temperature range for pure CO₂ and lean mixtures of CO₂ and air. The elements of the relaxation matrices were calculated at the appropriate physical conditions using the Exponential Power Gap (EPG) and Energy Corrected Sudden (ECS) scaling laws. We have compared our calculated low pressure line mixing parameters and the broadening coefficients with experimental results from two previous studies in our group available at 217, 234, 258 and 296 K. At all temperatures, the calculated broadening coefficients were also compared with those available in the HITRAN database.     

Absorption spectra of CO2 and CO2 near 1.05 μm

The absolute line intensities of the Fermi triad 2003i-00001 (i = 1, 2, 3) of ¹²C¹⁶O₂ and ¹³C¹⁶O₂ isotopic species of carbon dioxide were retrieved from Fourier-transform spectra recorded at Doppler limited resolution in the region 9200-9700 cm⁻¹. The accuracy of the line intensity determination is estimated to be better than 15% for most lines. The vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined. The global fittings of the observed line intensities within the framework of the effective operators method have been performed. The fitting results reproduce the data within experimental uncertainty.