合肥上空大气二氧化碳Raman激光雷达探测研究

Raman激光雷达是用于大气成分探测与特性研究的有效工具.介绍了中科院安徽光学精密机械研究所自行研制的一台用于测量低对流层大气CO2时空分布的Raman激光雷达系统,并进行了一系列观测实验和对比分析.系统选用波长355nm的紫外激光作为光源,利用光子计数卡双通道采集大气中N2和CO2的Raman后向散射信号与Li-7500型H2O/CO2分析仪进行对比标定,通过反演获得了大气CO2水平与垂直方向时空分布廓线,并且获得了合肥地区大气边界层CO2的夜变化趋势.结果表明,大气CO2在空间的分布相对均匀,Raman激光雷达与CO2分析仪变化趋势一致性较好,能够对大气CO2时空分布进行有效、连续的观测.     

基于遗传算法的CO2激光器三气体组份优化

应用遗传算法和数值求解CO₂激光动力学方程,以输出激光功率为目标函数,优化了典型封离型CO₂激光器三种主要工作气体(CO₂、N₂、He)的气体压强.对1.2m长谐振腔,在放电电压15kV条件下,三种气体的优化压强分别为PCO₂=1.15×133.3Pa、PN₂=7.36×133.3Pa、PH₂=13.33×133.3Pa.优化后激光功率可提高0.96倍.     

特定位点上CO2与(TiO2)n团簇相互作用的第一性原理研究

本文基于密度泛函理论系统地研究了(TiO₂)_n团簇上二氧化碳(CO₂)的吸附和活化性质. 计算结果表明,CO₂更倾向于吸附在(TiO₂)_n团簇的桥氧原子上,形成“化学吸附”碳酸盐络合物. 而CO更倾向于吸附到末端Ti-O的Ti原子上. 发现计算得到的碳酸盐振动频率值与实验获得的结果非常吻合,这表明配合物中CO₂的几何构型与其线性型相比,有微小的弯转. 通过对电子结构、电荷密度、电离势、HOMO-LUMO以及态密度的分析,证实了CO₂与团簇之间的电荷转移以及相互作用. 从预测的能量分布图来看,(TiO₂)_n团簇上的CO₂活化与结构密切有关,相比于块体的TiO₂,CO₂在团簇结构上更易于吸附和活化.     

光腔衰荡光谱法测量大气中的NO3和N2O5

本文应用基于二极管激光器的双路光腔衰荡光谱技术，分别对大气中NO₃和N₂O₅浓度进行监测. 通过使用实验室标准样校正有效吸收腔长比R_L和系统的总损耗系数?，并获得了NO₃有效吸收截面. 该装置在时间分辨率为1 s时，对NO₃的测量灵敏度达到1.1 pptv，N₂O₅被在线转换成NO₃，从而被另一路光腔衰荡光谱装置探测. 利用该装置，对合肥市区冬季夜间大气中的NO₃，N₂O₅浓度进行了实时监测. 通过对比一次大气快速清洁过程中氮氧化物、臭氧、PM_2.5等组分的浓度变化，讨论了大气环境下可能影响NO₃及N₂O₅浓度的因素.     

CO2激光器五种混合气体压强优化

 应用遗传算法,以输出激光功率为目标函数,优化确定了普通CO₂激光器五种工作气体（CO₂, N₂, He, Xe, H₂）的最佳充气量。对1.2m长谐振腔,在15kV放电条件下,优化的充气量分别为p_CO2=1.15×133.3Pa, p_N2=7.32×133.3Pa, p_He=12.95×133.3Pa, p_Xe=0.36×133.3Pa和p_H2=0.01×133.3Pa。优化后激光功率比未优化前可提高1.27倍。     

CO2激光成像雷达距离分辨率测距精度的分析与实验研究

分析了脉冲外差体制CO₂激光成像雷达系统的目标距离分辨率、测距精度和误差的主要来源.对于单个光脉冲测距来讲,信噪比(SNR)起伏引起的探测误差、脉冲前沿触发等概率分布以及脉冲建立时间的随机性等是激光脉冲外差测距的主要随机误差,其它随机误差在数量级上可忽略不计.同时利用现有的CO₂激光脉冲外差探测系统,进行了远目标测距对比实验,观测到了2355 m目标脉冲回波信号,并精确测量出CO₂光脉冲飞行的往返时间,该实验数据可用做系统误差的校正和补偿.     

大气NO3自由基损耗率和温度的关系

利用差分吸收光谱系统得到了大气NO₃、NO₂和O₃的浓度,基于NO₃损耗率和温度关系,获得了一种判定NO₃对于VOCs的大气氧化能力和清除大气中NO_x能力的新指示剂,该指示剂用动力学常量和单萜烯释放速率与温度关系来研究NO₃的损耗率．新指示剂应用于研究合肥郊区外场观测的NO₃的氧化能力,分析结果表明,在观测期间单萜烯对于NO₃的损耗贡献约为70%～80%.     

使用金属掺杂SnO2(110)作为表面催化剂的电催化CO2还原反应：通过调控Sn:O原子比例来控制产物

电催化CO₂还原反应可以产生HCOOH和CO,目前该反应是将可再生电力转化为化学能存储在燃料中的最有前景的方法之一. SnO₂作为将CO₂转换为HCOOH和CO的良好催化剂,其反应发生的晶面可以是不同的. 其中(110)面的SnO₂非常稳定,易于合成. 通过改变SnO₂(110)的Sn:O原子比例,得到了两种典型的SnO₂薄膜：完全氧化型(符合化学计量)和部分还原型. 本文研究了不同金属(Fe、Co、Ni、Cu、Ru、Rh、Pd、Ag、Os、Ir、Pt和Au)掺杂的SnO₂(110),发现在CO₂还原反应中这些材料的催化活性和选择性是不同的. 所有这些变化都可以通过调控(110)表面中Sn:O原子的比例来控制. 结果表明,化学计量型和部分还原型Cu/Ag掺杂的SnO₂(110)对CO₂还原反应具有不同的选择性. 具体而言,化学计量型的Cu/Ag掺杂的SnO₂(110)倾向于产生CO(g),而部分还原型的表面倾向于产生HCOOH(g). 此外,本文还考虑了CO₂还原的竞争析氢反应. 其中Ru、Rh、Pd、Os、Ir和Pt掺杂的SnO₂(110)催化剂对析氢反应具有较高的活性,其他催化剂对CO₂还原反应具有良好的催化作用.     

拉曼激光雷达探测低对流层大气二氧化碳分布

介绍了中国科学院安徽光学精密机械研究所研制成功的我国第一台测量低对流层大气CO2时空分布的拉曼激光雷达系统,选用波长355nm的紫外激光作为光源,利用光子计数卡双通道采集大气中N2和CO2的拉曼后向散射信号。详细分析了拉曼激光雷达系统的定标方法,提出采用Li7500型H2O/CO2分析仪与拉曼激光雷达系统进行对比与标定,结果显示激光雷达与CO2分析仪数据变化趋势一致性较好,激光雷达具有很高的探测灵敏度与准确性,通过线性拟合水平方向标定误差小于0.2%,垂直方向小于1.4%。由标定关系反演出大气中CO2的时空分布,给出了合肥西郊低对流层大气CO2水平方向0～2.0km与垂直方向0～2.5km分布的典型测量结果。     

Pd修饰Cu电极的电化学CO2还原

利用微分电化学质谱和电化学原位衰减全反射红外光谱技术探究了Cu和CuPd催化剂上CO₂和CO的电化学还原行为. 红外光谱观察到了生成甲醇、甲烷与乙烯的CH_x中间物种. 在CuPd电极CO₂还原过程中，红外光谱的CO吸附峰起始电位比Cu正移大约300 mV，说明CuPd能够有效促进CO₂还原；CO饱和溶液中，Cu和CuPd电极CO起始吸附电位基本相同；两电极上CO谱带出现的电位与CO₃^2-的谱带降低的电位基本相同，说明CO的吸附需要CO₃^2-的脱附. 利用电化学在线质谱发现在CuPd电极上CO还原产生CH₄和CH₃OH的起始电位比Cu电极正移约200 mV. 推测催化活性的提升可能是由于Pd的引入改变了Cu的d能带，且Pd吸附更多的H，从而促进CO₂还原，使CO能够与H结合并被深度还原.     

Analysis of influence of atmosphere extinction to Raman lidar monitoring CO2 concentration profile

Lidar （Light detection and ranging） system monitoring of the atmosphere is a novel and powerful technique tool. The Raman lidar is well established today as a leading research tool in the study of numerous important areas in the atmospheric sciences. In this paper, the principle of Raman lidar technique measurement CO2 concentration profile is presented and the errors caused by molecular and aerosol extinction for CO2 concentration profile measurement with Raman lidar are also presented. The standard atmosphere extinction profile and ＇real-time＇ Hefei area extinction profile are used to conduct correction and the corresponding results are yielded. Simulation results with standard atmosphere mode correction indicate that the errors caused by molecule and aerosol extinction should be counted for the reason that they could reach about 8 ppm and 5 ppm respectively. The relative error caused by Hefei area extinction correction could reach about 6%. The errors caused by the two components extinction influence could produce significant changes for CO2 concentration profile and need to be counted in data processing which could improve the measurement accuracies.     

探测大气中CO2的Raman激光雷达

基于大气激光后向散射光谱，研究和设计了探测大气CO₂浓度的Raman激光雷达,其发射机采用Nd∶YAG激光的三倍频354.7nm作为工作波长,发射的单脉冲能量350mJ,重复频率20Hz；接收机采用了光电倍增管(量子效率25%)和光子计数器(计数速率200MHz),探测CO₂的Raman散射371.66nm(频移1285cm^-1)信号,(1小时累加)近地面2.5km以内信噪比不小于8.采用组合滤光片来抑制强的354.7nm Mie-Rayleigh后向散射和氧气375.4nm Raman后向散射对信号的严重干扰. 比较分别来自大气CO₂和参考气体N₂的Raman后向散射回波,可反演出大气中CO₂的相对浓度. 关键词： 大气光学 激光雷达 Raman散射光谱 参考气体 Mie-Rayleigh散射     

A detection of atmospheric relative humidity profile by UV Raman lidar

A new spectroscopic filter constructed with a high-spectral-resolution grating and two narrow-band mirrors is designed to separate the elastic scattering and the vibrational Raman scattering spectra in an ultraviolet (UV) Raman lidar system. The density of humidity and water vapor mixing ratio are calculated from the vibrational Raman scattering signals of N₂ and H₂O. Water vapor mixing ratio is retrieved from this development. With this measured water vapor mixing ratio, the relative humidity is calculated with atmospheric temperature profile obtained by another Raman temperature lidar. Preliminary experiments and comparison results between lidar and radiosonde showed that the UV Raman lidar system has the capability for profiling the water vapor mixing ratio up to a height of 2 km with less than 10% of the uncertainty under the conditions of laser energy of 300 mJ and signal-averaging time of 10 min.     

Combined raman elastic-backscatter LIDAR for vertical profiling of moisture,aerosol extinction,backscatter, and LIDAR ratio

A combined Raman elastic-backscatter lidar has been developed. A XeCl excimer laser is used as the radiation source. Inelastic Raman backscatter signals are spectrally separated from the elastic signal with a filter or grating polychromator. Raman channels can be chosen to register signals from CO₂, O₂, N₂, and H₂O. Algorithms for the calculation of the water-vapor mixing ratio from the Raman signals and the particle extinction and backscatter coefficients from both elastic and inelastic backscatter signals are given. Nighttime measurements of the vertical humidity distribution up to the tropopause and of particle extinction, backscatter, and lidar ratio profiles in the boundary layer, in high-altitude water and ice clouds, and in the stratospheric aerosol layer are presented. Daytime boundary-layer measurements of moisture and particle extinction are made possible by the improved daylight suppression of the grating polychromator. Test measurements of the CO₂ mixing ratio indicate the problems for the Raman lidar technique in monitoring other trace gases than water vapor.     

A cavity ring-down analyzer for measuring atmospheric levels of methane, carbon dioxide, and water vapor

Researchers investigating global climate change need measurements of greenhouse gases with extreme precision and accuracy to enable the development and benchmarking of better climate models. Existing atmospheric monitors based on non-dispersive infrared (NDIR) sensors have known problems – they are non-linear, sensitive to water vapor concentration, and susceptible to drift. Many cannot easily be simultaneously calibrated across different sites to the level of accuracy required for use in atmospheric studies. We present results from field trials by Pennsylvania State University and the National Oceanographic and Atmospheric Administration (NOAA) of a newly available analyzer, based on cavity ring-down spectroscopy (CRDS), capable of measuring the concentrations of carbon dioxide (CO₂) and water vapor (H₂O). In addition, we present data from a new analyzer which measures CO₂, methane (CH₄), and H₂O. PACS  07.88.+y     

Laser spectroscopic monitoring of gas emission and measurements of the C/C isotope ratio in CO2 from a wood-based combustion

We report on the application of a compact and field-deployable instrument, based on a continuous-wave fiber-coupled Telecom external cavity diode laser, to measure the ¹³C/¹²C isotope ratio in CO₂ from a wood-based combustion. Carbon dioxide, the most important greenhouse gas, is a major product of combustion. The measurements of the ¹³C/¹²C isotopic ratio in CO₂ from combustion emission permit one to identify the CO₂ source and to study the temporal and spatial variations of pollution in the atmosphere. The average value of the ¹³CO₂/¹²CO₂ ratio is found to be (1.1011±0.0024)%. The corresponding δ-value relative to PDB standard is (−20.17±2.14)‰, which is in good agreement with the typical value of (−25±2)‰ for wood. Simultaneous monitoring of multiple species from gas emission has been performed using direct-absorption spectroscopy. The concentrations of C₂H₂, CO, CO₂ and H₂O were determined on the basis of integrated absorbance measured by least-squares fitting a Voigt lineshape to experimental absorption spectra.     

Optoacoustic gas analyzer based on a13C16O2 laser for multicomponent pollution of air

A computer-aided optoacoustic gas analyzer based on a continuous¹³C¹⁶C₂ laser for multicomponent pollution of atmospheric air is described. The analyzer has the ability to detect absorption of radiation by detected substances at the level of ∼1·10⁻⁹ cm⁻¹ at a time resolution of 30 sec. Results of an experiment on simultaneous detection of H₂O, CO₂, NO₂, NH₃, HNO₃, OCS, and C₂H₄ in the atmospheric air using 40 laser lines are presented. B. I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, 68, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 345–350, May–June, 1999.     

Atmospheric modelling using FASCOD to identify CO2 absorption bands and their suitability analysis in variable concentrations for remote sensing applications

Recent climate studies have proven that both temperature and CO₂ content of the earth's atmosphere followed a regular 100,000-year cycle of change and that they are closely correlated. Moreover, the observed increase of CO₂ in the atmosphere exceeds the predicted values extrapolated from historical data. Other than industrialization and rapid urbanization, geo-natural hazards such as leakage from hydrocarbon reservoirs and spontaneous combustion of coal contribute a considerable amount of CO₂ to the atmosphere. Several researchers have studied the possibilities and reliabilities of atmospheric CO₂ retrieval by the point-based method (nearly accurate but much localized) and globally (wider observation but many uncertainties). Radiative transfer codes, such as FASCOD (Fast Atmospheric Signature Code) with the HITRAN (High-Resolution Transmission) spectral database can simulate atmospheric transmission and path radiance with customized gas composition (CO₂, water vapour, CO, etc.) and concentration in order to understand the phenomena in a specific wavelength region. In the present study, a number of atmospheric models were constructed with different CO₂ concentrations (ppmv) with a combination of water vapour and other atmospheric gases such as CO, CH₄, N₂O, SO₂, etc., to find out the interference patterns of these gases over CO₂ absorption bands. The transmission features of these gas combinations were analysed by partial least-squares regression models. These models show that the most suitable CO₂ absorption bands are located around 2 μm, such as 1.998 and 2.001 μm. The spectral information derived from different concentrations of CO₂ can be fitted in multivariate models to predict the CO₂ concentration from spectral information in a controlled environment. Furthermore, the present study explores the sensitivity of some available remote sensing sensors in variable CO₂ concentrations for use in real world.